Crystal structure of 5-[bis-(4-eth-oxy-phenyl)amino]-thio-phene-2-carbaldehyde.

In the title compound, C21H21NO3S, the planes of the two benzene rings are nearly perpendicular to one another [dihedral angle = 84.50 (10)°] and they are oriented with respect to the plane of the thio-phene ring at dihedral angles of 59.15 (9) and 66.61 (9)°. In the crystal, mol-ecules are linked by weak C-H⋯O hydrogen bonds, forming supra-molecular chains propagating along the b-axis direction.

Related literature

For applications of thio­phene derivatives, see: Justin Thomas et al. (2008 ▶); Hansel et al. (2003 ▶); Mazzeo et al. (2003 ▶); Zhan et al. (2007 ▶); Bedworth et al. (1996 ▶); Raposo et al. (2011 ▶); Takekuma et al. (2005 ▶); Wurthner et al. (2002 ▶). For a related structure, see: Li et al. (2013 ▶).

Experimental

Crystal data

C21H21NO3S

M = 367.45

Monoclinic,

a = 11.101 (3) Å

b = 10.457 (3) Å

c = 17.326 (5) Å

β = 104.473 (4)°

V = 1947.5 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 296 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: ψ scan (SADABS; Bruker, 2002 ▶) T min = 0.946, T max = 0.964

13574 measured reflections

3430 independent reflections

2596 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.134

S = 0.93

3430 reflections

237 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814018984/xu5814sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018984/xu5814Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814018984/xu5814Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814018984/xu5814fig1.tif

The mol­ecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms

Click here for additional data file.

. DOI: 10.1107/S1600536814018984/xu5814fig2.tif

The infinite one-dimensional linear chain structure.

CCDC reference: 1016303

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

C21H21NO3S	F(000) = 776
Mr = 367.45	Dx = 1.253 Mg m−3
Monoclinic, P21/c	Melting point: 374 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.101 (3) Å	Cell parameters from 3509 reflections
b = 10.457 (3) Å	θ = 2.3–24.1°
c = 17.326 (5) Å	µ = 0.19 mm−1
β = 104.473 (4)°	T = 296 K
V = 1947.5 (10) Å3	Block, brown
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker SMART CCD area-detector diffractometer	3430 independent reflections
Radiation source: fine-focus sealed tube	2596 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
phi and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: ψ scan (SADABS; Bruker, 2002)	h = −13→13
Tmin = 0.946, Tmax = 0.964	k = −12→12
13574 measured reflections	l = −20→20

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H-atom parameters constrained
S = 0.93	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
3430 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.4645 (2)	0.2539 (2)	−0.07326 (14)	0.0795 (8)
H1A	0.3875	0.2164	−0.1023	0.119*
H1B	0.5294	0.1910	−0.0652	0.119*
H1C	0.4851	0.3245	−0.1030	0.119*
C2	0.4511 (2)	0.3002 (2)	0.00542 (12)	0.0613 (6)
H2A	0.4353	0.2288	0.0373	0.074*
H2B	0.5269	0.3425	0.0341	0.074*
C3	0.32106 (17)	0.44336 (17)	0.05611 (10)	0.0441 (4)
C4	0.22779 (19)	0.53578 (19)	0.04076 (11)	0.0528 (5)
H4	0.1875	0.5558	−0.0116	0.063*
C5	0.19465 (19)	0.59780 (19)	0.10249 (11)	0.0507 (5)
H5	0.1314	0.6585	0.0919	0.061*
C6	0.37954 (18)	0.41280 (18)	0.13421 (10)	0.0455 (5)
H6	0.4409	0.3502	0.1451	0.055*
C7	0.34628 (16)	0.47574 (18)	0.19585 (10)	0.0430 (4)
H7	0.3853	0.4547	0.2483	0.052*
C8	0.25621 (17)	0.56915 (17)	0.18073 (10)	0.0412 (4)
C9	0.0530 (2)	0.2588 (2)	0.59350 (13)	0.0724 (7)
H9A	−0.0314	0.2883	0.5840	0.109*
H9B	0.0908	0.2592	0.6497	0.109*
H9C	0.0537	0.1733	0.5733	0.109*
C10	0.1249 (2)	0.3460 (2)	0.55176 (12)	0.0575 (6)
H10A	0.1263	0.4323	0.5725	0.069*
H10B	0.2100	0.3163	0.5602	0.069*
C11	0.11284 (18)	0.4174 (2)	0.41918 (11)	0.0499 (5)
C12	0.21873 (17)	0.49193 (19)	0.44138 (11)	0.0514 (5)
H12	0.2638	0.4942	0.4944	0.062*
C13	0.25766 (17)	0.56310 (19)	0.38494 (11)	0.0486 (5)
H13	0.3301	0.6115	0.4000	0.058*
C14	0.0478 (2)	0.4155 (2)	0.34026 (12)	0.0660 (7)
H14	−0.0225	0.3642	0.3245	0.079*
C15	0.08529 (19)	0.4883 (2)	0.28423 (11)	0.0586 (6)
H15	0.0396	0.4870	0.2313	0.070*
C16	0.19027 (17)	0.56314 (18)	0.30648 (10)	0.0427 (5)
C17	0.25459 (15)	0.76413 (19)	0.25697 (9)	0.0397 (4)
C18	0.22906 (18)	0.84674 (18)	0.31280 (11)	0.0460 (5)
H18	0.1903	0.8222	0.3522	0.055*
C19	0.26784 (18)	0.97091 (18)	0.30347 (11)	0.0499 (5)
H19	0.2577	1.0379	0.3366	0.060*
C20	0.32226 (17)	0.98624 (18)	0.24143 (10)	0.0462 (5)
C21	0.3744 (2)	1.0975 (2)	0.21472 (12)	0.0575 (5)
H21	0.3685	1.1741	0.2408	0.069*
N1	0.22787 (14)	0.63697 (15)	0.24656 (8)	0.0450 (4)
O1	0.34853 (14)	0.38830 (14)	−0.00900 (7)	0.0573 (4)
O2	0.06415 (13)	0.34394 (14)	0.46905 (8)	0.0646 (4)
O3	0.42616 (15)	1.09978 (15)	0.16028 (9)	0.0707 (5)
S1	0.32839 (5)	0.84196 (5)	0.19335 (3)	0.0468 (2)

	U11	U22	U33	U12	U13	U23
C1	0.109 (2)	0.0737 (17)	0.0733 (15)	0.0184 (15)	0.0560 (15)	0.0055 (13)
C2	0.0756 (15)	0.0578 (13)	0.0612 (13)	0.0155 (12)	0.0369 (11)	0.0063 (11)
C3	0.0560 (12)	0.0403 (10)	0.0406 (9)	−0.0024 (9)	0.0208 (9)	−0.0021 (8)
C4	0.0657 (13)	0.0565 (13)	0.0369 (9)	0.0115 (10)	0.0142 (9)	0.0030 (9)
C5	0.0577 (12)	0.0504 (12)	0.0446 (10)	0.0109 (10)	0.0143 (9)	0.0024 (9)
C6	0.0505 (11)	0.0409 (11)	0.0479 (11)	0.0044 (9)	0.0176 (9)	0.0057 (8)
C7	0.0510 (11)	0.0421 (11)	0.0377 (9)	−0.0011 (9)	0.0143 (8)	0.0033 (8)
C8	0.0492 (11)	0.0393 (10)	0.0394 (9)	−0.0047 (8)	0.0192 (8)	−0.0039 (8)
C9	0.0796 (16)	0.0772 (17)	0.0695 (15)	0.0054 (13)	0.0353 (13)	0.0250 (13)
C10	0.0575 (13)	0.0674 (15)	0.0503 (12)	0.0064 (11)	0.0184 (10)	0.0179 (10)
C11	0.0493 (12)	0.0556 (13)	0.0482 (11)	−0.0079 (9)	0.0186 (9)	0.0051 (9)
C12	0.0481 (11)	0.0600 (13)	0.0435 (10)	−0.0046 (10)	0.0066 (9)	0.0085 (9)
C13	0.0437 (11)	0.0526 (12)	0.0490 (11)	−0.0091 (9)	0.0108 (9)	0.0030 (9)
C14	0.0627 (14)	0.0834 (18)	0.0522 (12)	−0.0346 (12)	0.0149 (10)	0.0007 (11)
C15	0.0595 (13)	0.0761 (15)	0.0400 (10)	−0.0205 (11)	0.0120 (9)	−0.0005 (10)
C16	0.0483 (11)	0.0436 (11)	0.0406 (9)	−0.0028 (8)	0.0192 (8)	−0.0010 (8)
C17	0.0399 (10)	0.0442 (11)	0.0361 (9)	0.0000 (8)	0.0118 (8)	0.0005 (8)
C18	0.0537 (12)	0.0484 (12)	0.0404 (10)	−0.0014 (9)	0.0201 (9)	−0.0033 (8)
C19	0.0617 (13)	0.0432 (11)	0.0459 (10)	0.0005 (9)	0.0154 (9)	−0.0083 (9)
C20	0.0526 (11)	0.0420 (11)	0.0436 (10)	0.0004 (9)	0.0113 (9)	0.0017 (8)
C21	0.0712 (14)	0.0447 (12)	0.0538 (12)	−0.0011 (10)	0.0105 (11)	0.0070 (10)
N1	0.0576 (10)	0.0412 (9)	0.0430 (9)	−0.0053 (7)	0.0254 (8)	−0.0027 (7)
O1	0.0763 (10)	0.0586 (9)	0.0431 (7)	0.0152 (8)	0.0264 (7)	−0.0011 (6)
O2	0.0617 (10)	0.0802 (11)	0.0531 (9)	−0.0194 (8)	0.0167 (7)	0.0158 (7)
O3	0.0902 (12)	0.0585 (10)	0.0688 (10)	−0.0028 (8)	0.0300 (9)	0.0201 (8)
S1	0.0575 (3)	0.0437 (3)	0.0457 (3)	−0.0001 (2)	0.0254 (2)	0.0024 (2)

C1—C2	1.488 (3)	C10—H10B	0.9700
C1—H1A	0.9600	C11—O2	1.364 (2)
C1—H1B	0.9600	C11—C14	1.378 (3)
C1—H1C	0.9600	C11—C12	1.383 (3)
C2—O1	1.437 (2)	C12—C13	1.381 (2)
C2—H2A	0.9700	C12—H12	0.9300
C2—H2B	0.9700	C13—C16	1.378 (2)
C3—O1	1.367 (2)	C13—H13	0.9300
C3—C6	1.384 (2)	C14—C15	1.378 (3)
C3—C4	1.393 (3)	C14—H14	0.9300
C4—C5	1.377 (2)	C15—C16	1.376 (3)
C4—H4	0.9300	C15—H15	0.9300
C5—C8	1.390 (2)	C16—N1	1.437 (2)
C5—H5	0.9300	C17—N1	1.364 (3)
C6—C7	1.381 (2)	C17—C18	1.378 (2)
C6—H6	0.9300	C17—S1	1.7321 (17)
C7—C8	1.375 (3)	C18—C19	1.390 (3)
C7—H7	0.9300	C18—H18	0.9300
C8—N1	1.443 (2)	C19—C20	1.368 (2)
C9—C10	1.510 (3)	C19—H19	0.9300
C9—H9A	0.9600	C20—C21	1.427 (3)
C9—H9B	0.9600	C20—S1	1.7330 (19)
C9—H9C	0.9600	C21—O3	1.221 (2)
C10—O2	1.423 (2)	C21—H21	0.9300
C10—H10A	0.9700
C2—C1—H1A	109.5	H10A—C10—H10B	108.5
C2—C1—H1B	109.5	O2—C11—C14	115.37 (17)
H1A—C1—H1B	109.5	O2—C11—C12	125.80 (17)
C2—C1—H1C	109.5	C14—C11—C12	118.83 (17)
H1A—C1—H1C	109.5	C13—C12—C11	120.11 (17)
H1B—C1—H1C	109.5	C13—C12—H12	119.9
O1—C2—C1	107.78 (18)	C11—C12—H12	119.9
O1—C2—H2A	110.2	C16—C13—C12	120.64 (17)
C1—C2—H2A	110.2	C16—C13—H13	119.7
O1—C2—H2B	110.2	C12—C13—H13	119.7
C1—C2—H2B	110.2	C15—C14—C11	121.07 (19)
H2A—C2—H2B	108.5	C15—C14—H14	119.5
O1—C3—C6	124.24 (17)	C11—C14—H14	119.5
O1—C3—C4	116.30 (16)	C16—C15—C14	120.04 (18)
C6—C3—C4	119.45 (16)	C16—C15—H15	120.0
C5—C4—C3	120.57 (17)	C14—C15—H15	120.0
C5—C4—H4	119.7	C15—C16—C13	119.28 (17)
C3—C4—H4	119.7	C15—C16—N1	118.78 (16)
C4—C5—C8	119.62 (18)	C13—C16—N1	121.92 (16)
C4—C5—H5	120.2	N1—C17—C18	128.87 (16)
C8—C5—H5	120.2	N1—C17—S1	119.71 (13)
C7—C6—C3	119.69 (17)	C18—C17—S1	111.41 (15)
C7—C6—H6	120.2	C17—C18—C19	112.33 (17)
C3—C6—H6	120.2	C17—C18—H18	123.8
C8—C7—C6	120.89 (16)	C19—C18—H18	123.8
C8—C7—H7	119.6	C20—C19—C18	114.29 (17)
C6—C7—H7	119.6	C20—C19—H19	122.9
C7—C8—C5	119.72 (16)	C18—C19—H19	122.9
C7—C8—N1	119.36 (15)	C19—C20—C21	130.17 (19)
C5—C8—N1	120.92 (17)	C19—C20—S1	110.73 (14)
C10—C9—H9A	109.5	C21—C20—S1	119.08 (15)
C10—C9—H9B	109.5	O3—C21—C20	125.0 (2)
H9A—C9—H9B	109.5	O3—C21—H21	117.5
C10—C9—H9C	109.5	C20—C21—H21	117.5
H9A—C9—H9C	109.5	C17—N1—C16	121.39 (14)
H9B—C9—H9C	109.5	C17—N1—C8	120.02 (14)
O2—C10—C9	107.39 (18)	C16—N1—C8	117.85 (15)
O2—C10—H10A	110.2	C3—O1—C2	117.19 (15)
C9—C10—H10A	110.2	C11—O2—C10	117.79 (15)
O2—C10—H10B	110.2	C17—S1—C20	91.23 (9)
C9—C10—H10B	110.2
O1—C3—C4—C5	−179.17 (18)	C19—C20—C21—O3	176.6 (2)
C6—C3—C4—C5	0.8 (3)	S1—C20—C21—O3	−1.2 (3)
C3—C4—C5—C8	1.0 (3)	C18—C17—N1—C16	−13.9 (3)
O1—C3—C6—C7	178.88 (17)	S1—C17—N1—C16	167.25 (13)
C4—C3—C6—C7	−1.1 (3)	C18—C17—N1—C8	176.16 (18)
C3—C6—C7—C8	−0.4 (3)	S1—C17—N1—C8	−2.7 (2)
C6—C7—C8—C5	2.2 (3)	C15—C16—N1—C17	130.0 (2)
C6—C7—C8—N1	−177.18 (16)	C13—C16—N1—C17	−51.4 (3)
C4—C5—C8—C7	−2.5 (3)	C15—C16—N1—C8	−59.9 (2)
C4—C5—C8—N1	176.91 (17)	C13—C16—N1—C8	118.7 (2)
O2—C11—C12—C13	−179.35 (19)	C7—C8—N1—C17	113.3 (2)
C14—C11—C12—C13	0.1 (3)	C5—C8—N1—C17	−66.1 (2)
C11—C12—C13—C16	1.5 (3)	C7—C8—N1—C16	−57.0 (2)
O2—C11—C14—C15	178.1 (2)	C5—C8—N1—C16	123.60 (19)
C12—C11—C14—C15	−1.4 (4)	C6—C3—O1—C2	−4.8 (3)
C11—C14—C15—C16	1.0 (4)	C4—C3—O1—C2	175.18 (17)
C14—C15—C16—C13	0.7 (3)	C1—C2—O1—C3	−179.38 (18)
C14—C15—C16—N1	179.3 (2)	C14—C11—O2—C10	−177.71 (19)
C12—C13—C16—C15	−1.9 (3)	C12—C11—O2—C10	1.8 (3)
C12—C13—C16—N1	179.50 (18)	C9—C10—O2—C11	179.51 (18)
N1—C17—C18—C19	−178.39 (18)	N1—C17—S1—C20	178.13 (15)
S1—C17—C18—C19	0.5 (2)	C18—C17—S1—C20	−0.88 (14)
C17—C18—C19—C20	0.3 (3)	C19—C20—S1—C17	1.03 (15)
C18—C19—C20—C21	−178.9 (2)	C21—C20—S1—C17	179.24 (16)
C18—C19—C20—S1	−1.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3i	0.97	2.55	3.470 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O3i	0.97	2.55	3.470 (3)	159

Symmetry code: (i) .