4-(2-Thienylmethyl­eneamino)benzoic acid

Cui, H.; Tao, X.

doi:10.1107/S1600536809039208

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2635

https://doi.org/10.1107/S1600536809039208

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4-(2-Thienylmethyleneamino)benzoic acid

Hui Cui ^a and Xuquan Tao ^b ^*

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

(Received 15 September 2009; accepted 27 September 2009; online 3 October 2009)

In the title molecule, C₁₂H₉NO₂S, the dihedral angle between benzene and thiophene rings is 41.91 (8)°. The crystal packing exhibits short intermolecular O—H⋯O and C—H⋯O hydrogen-bonding contacts.

Related literature

For the synthesis of substituted thiophenes, see: Koike et al. (1999 ). For the anticancer activity of Schiff bases, see: Chakraborty & Patel (1996 ). For a related structure, see: Hu et al. (2008 ).

Experimental

Crystal data

C₁₂H₉NO₂S
M_r = 231.26
Monoclinic, P 2₁ /c
a = 3.8801 (3) Å
b = 10.0849 (11) Å
c = 27.380 (3) Å
β = 93.185 (1)°
V = 1069.74 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 298 K
0.43 × 0.20 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.888, T_max = 0.967
5213 measured reflections
1887 independent reflections
1496 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.140
S = 1.09
1887 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.83	2.641 (3)	172
C3—H3⋯O2ⁱⁱ	0.93	2.52	3.441 (4)	169
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x-1, y-1, z.

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: https://doi.org/10.1107/S1600536809039208/bq2161sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039208/bq2161Isup2.hkl

checkCIF report

Comment top

The synthesis of substituted thiophenes has attracted a great deal of interest over the years due to their presence in natural products (Koike, et al., 1999). Moreover, Schiff bases derived from a large number of carbonyl compounds and amines. It has been shown that Schiff base compounds have strong anticancer activity (Chakraborty et al., 1996).

Here, we report the synthesis and crystal structure of a new flexible Schiff-base compound 4-aminobenzoic acid thiophene-2-carbaldehyde schiff base, (I). 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 C(1)=N(1) bond length of 1.277 (4) Å, conform to the usual value for a C=N double bond. Each half of the molecule displays a trans configuration across the C=N double bond.

In the crystal structure, the dihedral angle between the benzene ring and the thiophene ring is 41.91 (8)°. Moreover, the two-dimensional network structures were formed by the intermolecular O—H···O and C-H···O H-bond interactions (Figure 2 and Table 1).

Related literature top

For the synthesis of substituted thiophenes, see: Koike et al. (1999). For the anticancer activity of Schiff bases, see: Chakraborty et al. (1996). For a related structure, see: Hu et al. (2008).

Experimental top

4-Aminobenzoic acid (10 mmol), thiophene-2-carbaldehyde (10 mmol) and 20 ml ethanol were mixed in 50 ml flask. After stirring 3 h at 303 K, the resulting mixture was recrystalized from ethanol, affording the title compound as a red crystalline solid. Elemental analysis: calculated for C₁₂H₉N₂OS: C 62.32, H 3.92, N 6.06%; found: C 62.38, H 4.14, N 6.17%.

Structure description top

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) with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of (I)

4-(2-Thienylmethyleneamino)benzoic acid top

Crystal data top

C₁₂H₉NO₂S	F(000) = 480
M_r = 231.26	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1697 reflections
a = 3.8801 (3) Å	θ = 3.0–24.6°
b = 10.0849 (11) Å	µ = 0.28 mm⁻¹
c = 27.380 (3) Å	T = 298 K
β = 93.185 (1)°	Block, red
V = 1069.74 (18) Å³	0.43 × 0.20 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1887 independent reflections
Radiation source: fine-focus sealed tube	1496 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
φ and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.888, T_max = 0.967	k = −12→9
5213 measured reflections	l = −29→32

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0616P)² + 0.4613P] where P = (F_o² + 2F_c²)/3
1887 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₂H₉NO₂S	V = 1069.74 (18) Å³
M_r = 231.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8801 (3) Å	µ = 0.28 mm⁻¹
b = 10.0849 (11) Å	T = 298 K
c = 27.380 (3) Å	0.43 × 0.20 × 0.12 mm
β = 93.185 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1887 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1496 reflections with I > 2σ(I)
T_min = 0.888, T_max = 0.967	R_int = 0.044
5213 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.09	Δρ_max = 0.35 e Å⁻³
1887 reflections	Δρ_min = −0.22 e Å⁻³
145 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
N1	0.4137 (7)	0.4083 (2)	0.34590 (9)	0.0410 (6)
O1	0.9679 (7)	0.8245 (2)	0.50746 (8)	0.0580 (7)
H1	1.0383	0.8943	0.5197	0.087*
O2	0.7517 (7)	0.9632 (2)	0.45013 (7)	0.0543 (6)
S1	0.3211 (2)	0.18720 (8)	0.26947 (3)	0.0476 (3)
C1	0.2843 (8)	0.3008 (3)	0.36133 (11)	0.0438 (8)
H1A	0.2297	0.2954	0.3939	0.053*
C2	0.2192 (8)	0.1869 (3)	0.32997 (10)	0.0389 (7)
C3	0.0828 (9)	0.0673 (3)	0.34261 (11)	0.0472 (8)
H3	0.0114	0.0483	0.3737	0.057*
C4	0.0618 (9)	−0.0239 (3)	0.30361 (12)	0.0506 (9)
H4	−0.0252	−0.1094	0.3061	0.061*
C5	0.1821 (9)	0.0267 (3)	0.26221 (12)	0.0515 (9)
H5	0.1888	−0.0202	0.2330	0.062*
C6	0.8065 (8)	0.8483 (3)	0.46603 (10)	0.0397 (7)
C7	0.6845 (7)	0.7322 (3)	0.43688 (9)	0.0354 (7)
C8	0.7347 (8)	0.6033 (3)	0.45455 (10)	0.0403 (7)
H8	0.8320	0.5902	0.4860	0.048*
C9	0.6413 (8)	0.4952 (3)	0.42586 (10)	0.0419 (8)
H9	0.6774	0.4098	0.4379	0.050*
C10	0.4922 (7)	0.5141 (3)	0.37856 (10)	0.0358 (7)
C11	0.4398 (8)	0.6428 (3)	0.36128 (10)	0.0407 (7)
H11	0.3413	0.6561	0.3299	0.049*
C12	0.5320 (8)	0.7508 (3)	0.39001 (10)	0.0395 (7)
H12	0.4924	0.8362	0.3781	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0479 (16)	0.0341 (14)	0.0407 (14)	−0.0028 (12)	−0.0002 (11)	−0.0039 (11)
O1	0.0861 (18)	0.0389 (13)	0.0463 (13)	−0.0045 (12)	−0.0194 (12)	−0.0047 (10)
O2	0.0839 (18)	0.0321 (12)	0.0455 (12)	−0.0027 (12)	−0.0094 (11)	−0.0006 (10)
S1	0.0579 (6)	0.0426 (5)	0.0424 (5)	−0.0005 (4)	0.0042 (4)	−0.0011 (3)
C1	0.0488 (19)	0.0427 (18)	0.0404 (16)	0.0005 (15)	0.0060 (14)	−0.0051 (14)
C2	0.0392 (17)	0.0358 (16)	0.0414 (16)	0.0019 (14)	−0.0008 (13)	−0.0027 (13)
C3	0.055 (2)	0.0433 (19)	0.0432 (17)	−0.0036 (16)	0.0038 (15)	0.0041 (14)
C4	0.055 (2)	0.0341 (17)	0.062 (2)	−0.0043 (15)	−0.0028 (17)	−0.0020 (15)
C5	0.057 (2)	0.0443 (19)	0.052 (2)	0.0033 (17)	−0.0097 (16)	−0.0126 (16)
C6	0.0469 (19)	0.0373 (17)	0.0349 (15)	0.0007 (14)	0.0025 (13)	−0.0004 (13)
C7	0.0389 (17)	0.0316 (15)	0.0356 (15)	−0.0002 (13)	0.0011 (12)	−0.0021 (12)
C8	0.0497 (19)	0.0375 (16)	0.0327 (15)	0.0014 (14)	−0.0056 (13)	0.0000 (13)
C9	0.052 (2)	0.0308 (16)	0.0426 (17)	0.0016 (14)	−0.0003 (14)	0.0016 (13)
C10	0.0376 (17)	0.0364 (16)	0.0335 (15)	−0.0015 (13)	0.0025 (12)	−0.0049 (12)
C11	0.0470 (19)	0.0400 (17)	0.0341 (15)	−0.0011 (15)	−0.0058 (13)	0.0013 (13)
C12	0.0477 (18)	0.0302 (15)	0.0403 (16)	0.0011 (14)	−0.0005 (13)	0.0020 (13)

Geometric parameters (Å, º) top

N1—C1	1.277 (4)	C4—H4	0.9300
N1—C10	1.414 (3)	C5—H5	0.9300
O1—C6	1.287 (3)	C6—C7	1.480 (4)
O1—H1	0.8200	C7—C12	1.396 (4)
O2—C6	1.252 (3)	C7—C8	1.397 (4)
S1—C5	1.714 (3)	C8—C9	1.380 (4)
S1—C2	1.724 (3)	C8—H8	0.9300
C1—C2	1.448 (4)	C9—C10	1.402 (4)
C1—H1A	0.9300	C9—H9	0.9300
C2—C3	1.369 (4)	C10—C11	1.392 (4)
C3—C4	1.408 (4)	C11—C12	1.379 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.350 (4)	C12—H12	0.9300

C1—N1—C10	120.4 (3)	O1—C6—C7	116.9 (3)
C6—O1—H1	109.5	C12—C7—C8	119.2 (3)
C5—S1—C2	91.28 (15)	C12—C7—C6	119.8 (3)
N1—C1—C2	122.4 (3)	C8—C7—C6	121.0 (2)
N1—C1—H1A	118.8	C9—C8—C7	120.7 (3)
C2—C1—H1A	118.8	C9—C8—H8	119.6
C3—C2—C1	127.3 (3)	C7—C8—H8	119.6
C3—C2—S1	110.9 (2)	C8—C9—C10	120.0 (3)
C1—C2—S1	121.8 (2)	C8—C9—H9	120.0
C2—C3—C4	113.0 (3)	C10—C9—H9	120.0
C2—C3—H3	123.5	C11—C10—C9	119.0 (3)
C4—C3—H3	123.5	C11—C10—N1	117.8 (2)
C5—C4—C3	112.4 (3)	C9—C10—N1	123.0 (3)
C5—C4—H4	123.8	C12—C11—C10	120.9 (3)
C3—C4—H4	123.8	C12—C11—H11	119.5
C4—C5—S1	112.4 (2)	C10—C11—H11	119.5
C4—C5—H5	123.8	C11—C12—C7	120.1 (3)
S1—C5—H5	123.8	C11—C12—H12	120.0
O2—C6—O1	123.0 (3)	C7—C12—H12	120.0
O2—C6—C7	120.1 (3)

C10—N1—C1—C2	−176.1 (3)	O1—C6—C7—C8	1.8 (4)
N1—C1—C2—C3	179.9 (3)	C12—C7—C8—C9	1.2 (5)
N1—C1—C2—S1	1.4 (4)	C6—C7—C8—C9	−175.6 (3)
C5—S1—C2—C3	−0.4 (3)	C7—C8—C9—C10	−0.4 (5)
C5—S1—C2—C1	178.3 (3)	C8—C9—C10—C11	−0.1 (4)
C1—C2—C3—C4	−178.4 (3)	C8—C9—C10—N1	175.2 (3)
S1—C2—C3—C4	0.2 (4)	C1—N1—C10—C11	−143.8 (3)
C2—C3—C4—C5	0.2 (4)	C1—N1—C10—C9	40.8 (4)
C3—C4—C5—S1	−0.5 (4)	C9—C10—C11—C12	−0.1 (5)
C2—S1—C5—C4	0.5 (3)	N1—C10—C11—C12	−175.7 (3)
O2—C6—C7—C12	4.9 (4)	C10—C11—C12—C7	0.9 (5)
O1—C6—C7—C12	−175.0 (3)	C8—C7—C12—C11	−1.5 (5)
O2—C6—C7—C8	−178.2 (3)	C6—C7—C12—C11	175.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.83	2.641 (3)	172
C3—H3···O2ⁱⁱ	0.93	2.52	3.441 (4)	169

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₉NO₂S
M_r	231.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	3.8801 (3), 10.0849 (11), 27.380 (3)
β (°)	93.185 (1)
V (Å³)	1069.74 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.43 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.888, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	5213, 1887, 1496
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.140, 1.09
No. of reflections	1887
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.22

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.83	2.641 (3)	172.0
C3—H3···O2ⁱⁱ	0.93	2.52	3.441 (4)	169.3

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x−1, y−1, z.

Acknowledgements

The authors acknowledge financial support by Liaocheng University (X20090101).

References

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