(Z)-2-Meth­oxy-N-[(5-nitro­thio­phen-2-yl)methyl­idene]aniline

Kan Kaynar, N.; Gümüs, S.; Ağar, E.; Büyükgüngör, O.; Yavuz, M.

doi:10.1107/S160053681200044X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o393

doi:10.1107/S160053681200044X

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(Z)-2-Methoxy-N-[(5-nitrothiophen-2-yl)methylidene]aniline

Nihal Kan Kaynar,^a ^* Sümeyye Gümüs,^b Erbil Ağar,^b Orhan Büyükgüngör ^a and Metin Yavuz ^c

^aDepartment of Physics, Faculty of Arts & Science, Ondokuz Mayis University, TR-55139 Kurupelit-Samsun, Turkey, ^bDepartment of Chemistry, Faculty of Arts & Science, Ondokuz Mayis University, 55139 Samsun, Turkey, and ^cDepartment of Physics, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey, and, Faculty of Technology, Amasya University, TR-05100 Amasya, Turkey
^*Correspondence e-mail: nihal_kan84@windowslive.com

(Received 30 December 2011; accepted 5 January 2012; online 14 January 2012)

The dihedral angle between the benzene and thiophene rings in the title compound, C₁₂H₁₀N₂O₃S, is 27.94 (13)°. An intermolecular C—H⋯π interaction contributes to the stability of the crystal structure.

Related literature

For the biological properties of Schiff bases, see: Barton & Ollis (1979 ); Layer (1963 ); Ingold (1969 ), for their industrial properties, see: Taggi et al. (2002 ) and for their reaction properties, see: Aydoğan et al. (2001 ). For related structures, see: Ağar et al. (2010 ); Tanak et al. (2009 ); Ceylan et al. (2011 ).

Experimental

Crystal data

C₁₂H₁₀N₂O₃S
M_r = 262.28
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.6825 (6) Å
b = 7.7926 (5) Å
c = 23.7180 (12) Å
V = 1235.09 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.59 × 0.39 × 0.05 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.974, T_max = 0.974
5645 measured reflections
2599 independent reflections
1799 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.069
S = 0.93
2599 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1067 Friedel pairs
Flack parameter: −0.04 (8)

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C6–C11 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cg2ⁱ	0.93	2.77	3.605 (3)	149
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681200044X/bt5776sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200044X/bt5776Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200044X/bt5776Isup3.cml

checkCIF report

Comment top

Schiff bases, i.e., compounds having a double C=N bond, are used as starting materials in the synthesis of important drugs, such as antibiotics and antiallergic, antiphlogistic, and antitumor substances (Barton et al., 1979; Layer, 1963; Ingold 1969). On the industrial scale, they have a wide range of applications, such as dyes and pigments (Taggi et al., 2002). Schiff bases have also been employed as ligands for the complexation of metal ions (Aydoğan et al., 2001).

The molecular structure of the title compound is shown on Fig. 1. The dihedral angle between the C10—C13/S1 nitrothiophene and the C1—C6 phenyl ring is 27.94 (13)°. The deviation from planarity may be due to steric repulsion between the methylene group and phenyl ring. The length of the C5=N2 double bond is 1.266 (3) Å, slightly shorter than standard 1.28 Å value of a C=N double bond and consistent with related structures (Ağar et al., 2010; Tanak et al., 2009; Ceylan et al., 2011).

The crystal structure is stabilized by an intermolecular C—H···π interaction (C10—H10···Cg2). No significant π—π interactions are observed in the crystal structure.

Related literature top

For the biological properties of Schiff bases, see: Barton & Ollis (1979); Layer (1963); Ingold (1969), for their industrial properties, see: Taggi et al. (2002) and for their reaction properties, see: Aydoğan et al. (2001). For related structures, see: Ağar et al. (2010); Tanak et al. (2009); Ceylan et al. (2011).

Experimental top

The compound (Z)—N-(2-methoxyphenyl)-1-(5-nitrothiophen-2-yl)methanimine was prepared by reflux a mixture of a solution containing 5-nitro-2-thiophene-carboxaldehyde (0.0078 g 0.050 mmol) in 20 ml e thanol and a solution containing o-Anisidine (0.0062 g 0.050 mmol) in 20 ml e thanol. The reaction mixture was stirred for 1 hunder reflux. The crystals of (Z)—N-(2-methoxyphenyl)-1-(5-nitrothiophen-2-yl)methanimine suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield % 76; 85–87 °C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability diplacement ellipsoids.

(Z)-2-Methoxy-N-[(5-nitrothiophen-2-yl)methylidene]aniline top

Crystal data top

C₁₂H₁₀N₂O₃S	F(000) = 544
M_r = 262.28	D_x = 1.411 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6785 reflections
a = 6.6825 (6) Å	θ = 2.6–27.2°
b = 7.7926 (5) Å	µ = 0.26 mm⁻¹
c = 23.7180 (12) Å	T = 296 K
V = 1235.09 (15) Å³	Plate, yellow
Z = 4	0.59 × 0.39 × 0.05 mm

Data collection top

Stoe IPDS II diffractometer	2599 independent reflections
Radiation source: fine-focus sealed tube	1799 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.8°, θ_min = 2.8°
rotation method scans	h = −6→8
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −9→9
T_min = 0.974, T_max = 0.974	l = −29→29
5645 measured reflections

Refinement top

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0284P)²] where P = (F_o² + 2F_c²)/3
S = 0.93	(Δ/σ)_max < 0.001
2599 reflections	Δρ_max = 0.12 e Å⁻³
163 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1067 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (8)

Crystal data top

C₁₂H₁₀N₂O₃S	V = 1235.09 (15) Å³
M_r = 262.28	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.6825 (6) Å	µ = 0.26 mm⁻¹
b = 7.7926 (5) Å	T = 296 K
c = 23.7180 (12) Å	0.59 × 0.39 × 0.05 mm

Data collection top

Stoe IPDS II diffractometer	2599 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1799 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.974	R_int = 0.038
5645 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 0.12 e Å⁻³
S = 0.93	Δρ_min = −0.21 e Å⁻³
2599 reflections	Absolute structure: Flack (1983), 1067 Friedel pairs
163 parameters	Absolute structure parameter: −0.04 (8)
0 restraints

Special details top

Experimental. 108 frames, detector distance = 120 mm

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	0.93052 (10)	0.80791 (7)	0.16132 (3)	0.06181 (17)
O4	0.4298 (3)	0.59180 (17)	0.04012 (7)	0.0711 (5)
C7	0.5822 (4)	0.2075 (3)	0.11420 (10)	0.0649 (6)
H7	0.6780	0.1749	0.1405	0.078*
C11	0.4265 (4)	0.4242 (3)	0.05670 (10)	0.0572 (5)
C6	0.5750 (4)	0.3765 (3)	0.09543 (9)	0.0568 (6)
N2	0.7021 (4)	0.5066 (2)	0.11656 (8)	0.0613 (5)
C1	1.1502 (4)	0.8578 (3)	0.19332 (10)	0.0561 (6)
O1	1.3451 (3)	1.0633 (2)	0.23403 (9)	0.0968 (7)
C8	0.4476 (5)	0.0878 (3)	0.09384 (11)	0.0735 (7)
H8	0.4546	−0.0255	0.1060	0.088*
N1	1.1877 (4)	1.0325 (3)	0.20966 (9)	0.0695 (6)
C5	0.8791 (4)	0.4701 (3)	0.13135 (10)	0.0614 (6)
H5	0.9268	0.3592	0.1259	0.074*
C9	0.3052 (5)	0.1357 (3)	0.05614 (12)	0.0744 (8)
H9	0.2147	0.0546	0.0428	0.089*
C4	1.0087 (3)	0.5975 (3)	0.15657 (11)	0.0562 (6)
O2	1.0599 (4)	1.1402 (2)	0.19817 (8)	0.0883 (6)
C10	0.2928 (4)	0.3033 (3)	0.03729 (10)	0.0671 (6)
H10	0.1944	0.3343	0.0115	0.081*
C3	1.1934 (4)	0.5742 (3)	0.17897 (11)	0.0675 (7)
H3	1.2582	0.4686	0.1798	0.081*
C2	1.2765 (4)	0.7248 (3)	0.20070 (11)	0.0685 (7)
H2	1.4013	0.7323	0.2178	0.082*
C13	0.2741 (5)	0.6489 (3)	0.00482 (13)	0.0897 (9)
H13A	0.2933	0.7682	−0.0037	0.135*
H13B	0.1481	0.6339	0.0236	0.135*
H13C	0.2748	0.5837	−0.0295	0.135*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0602 (3)	0.0558 (3)	0.0694 (4)	0.0056 (3)	−0.0122 (4)	0.0013 (3)
O4	0.0705 (11)	0.0537 (8)	0.0889 (13)	−0.0040 (9)	−0.0184 (12)	0.0056 (8)
C7	0.0688 (15)	0.0610 (12)	0.0650 (14)	−0.0041 (14)	0.0017 (15)	0.0057 (12)
C11	0.0587 (13)	0.0531 (11)	0.0598 (14)	−0.0041 (12)	0.0017 (14)	−0.0040 (9)
C6	0.0613 (14)	0.0544 (11)	0.0548 (14)	−0.0042 (12)	0.0049 (14)	−0.0065 (9)
N2	0.0669 (15)	0.0554 (10)	0.0615 (12)	−0.0027 (10)	−0.0049 (11)	−0.0060 (9)
C1	0.0587 (15)	0.0552 (12)	0.0543 (14)	−0.0048 (10)	−0.0054 (12)	0.0014 (10)
O1	0.0939 (17)	0.0998 (13)	0.0967 (15)	−0.0252 (12)	−0.0188 (13)	−0.0225 (11)
C8	0.087 (2)	0.0523 (12)	0.0808 (19)	−0.0052 (15)	0.0142 (18)	0.0050 (12)
N1	0.0762 (16)	0.0724 (14)	0.0598 (14)	−0.0166 (13)	−0.0058 (12)	−0.0045 (10)
C5	0.0612 (19)	0.0548 (12)	0.0681 (16)	0.0022 (11)	−0.0007 (13)	−0.0027 (11)
C9	0.0749 (18)	0.0668 (15)	0.0813 (19)	−0.0151 (14)	0.0057 (18)	−0.0075 (13)
C4	0.0531 (14)	0.0539 (11)	0.0616 (15)	0.0036 (9)	−0.0017 (12)	−0.0006 (11)
O2	0.1080 (15)	0.0631 (10)	0.0937 (14)	0.0073 (12)	−0.0122 (15)	−0.0038 (9)
C10	0.0635 (15)	0.0672 (14)	0.0706 (16)	−0.0065 (13)	−0.0015 (14)	−0.0088 (13)
C3	0.0599 (17)	0.0611 (13)	0.0816 (19)	0.0080 (13)	−0.0018 (14)	0.0015 (12)
C2	0.0580 (15)	0.0760 (16)	0.0714 (16)	−0.0016 (13)	−0.0133 (13)	0.0070 (13)
C13	0.081 (2)	0.0754 (16)	0.112 (2)	0.0061 (15)	−0.0289 (19)	0.0128 (15)

Geometric parameters (Å, º) top

S1—C1	1.698 (2)	C8—H8	0.9300
S1—C4	1.725 (2)	N1—O2	1.228 (3)
O4—C11	1.364 (2)	C5—C4	1.447 (3)
O4—C13	1.408 (3)	C5—H5	0.9300
C7—C8	1.383 (4)	C9—C10	1.383 (3)
C7—C6	1.391 (3)	C9—H9	0.9300
C7—H7	0.9300	C4—C3	1.356 (3)
C11—C10	1.378 (3)	C10—H10	0.9300
C11—C6	1.402 (3)	C3—C2	1.397 (3)
C6—N2	1.414 (3)	C3—H3	0.9300
N2—C5	1.266 (3)	C2—H2	0.9300
C1—C2	1.348 (3)	C13—H13A	0.9600
C1—N1	1.437 (3)	C13—H13B	0.9600
O1—N1	1.224 (3)	C13—H13C	0.9600
C8—C9	1.358 (4)

C1—S1—C4	89.14 (11)	C4—C5—H5	119.3
C11—O4—C13	117.5 (2)	C8—C9—C10	120.9 (2)
C8—C7—C6	120.3 (2)	C8—C9—H9	119.5
C8—C7—H7	119.9	C10—C9—H9	119.5
C6—C7—H7	119.9	C3—C4—C5	127.9 (2)
O4—C11—C10	124.7 (2)	C3—C4—S1	112.20 (18)
O4—C11—C6	115.5 (2)	C5—C4—S1	119.86 (17)
C10—C11—C6	119.8 (2)	C11—C10—C9	119.9 (2)
C7—C6—C11	119.0 (2)	C11—C10—H10	120.0
C7—C6—N2	123.0 (2)	C9—C10—H10	120.0
C11—C6—N2	117.87 (19)	C4—C3—C2	113.2 (2)
C5—N2—C6	119.9 (2)	C4—C3—H3	123.4
C2—C1—N1	125.7 (2)	C2—C3—H3	123.4
C2—C1—S1	115.04 (17)	C1—C2—C3	110.4 (2)
N1—C1—S1	119.23 (18)	C1—C2—H2	124.8
C9—C8—C7	120.0 (2)	C3—C2—H2	124.8
C9—C8—H8	120.0	O4—C13—H13A	109.5
C7—C8—H8	120.0	O4—C13—H13B	109.5
O1—N1—O2	124.6 (2)	H13A—C13—H13B	109.5
O1—N1—C1	117.6 (2)	O4—C13—H13C	109.5
O2—N1—C1	117.8 (2)	H13A—C13—H13C	109.5
N2—C5—C4	121.3 (2)	H13B—C13—H13C	109.5
N2—C5—H5	119.3

C13—O4—C11—C10	6.3 (4)	S1—C1—N1—O2	−2.0 (3)
C13—O4—C11—C6	−175.0 (2)	C6—N2—C5—C4	−175.9 (2)
C8—C7—C6—C11	1.5 (4)	C7—C8—C9—C10	0.4 (4)
C8—C7—C6—N2	176.9 (2)	N2—C5—C4—C3	173.5 (3)
O4—C11—C6—C7	−179.7 (2)	N2—C5—C4—S1	−5.6 (3)
C10—C11—C6—C7	−1.0 (3)	C1—S1—C4—C3	0.1 (2)
O4—C11—C6—N2	4.6 (3)	C1—S1—C4—C5	179.4 (2)
C10—C11—C6—N2	−176.7 (2)	O4—C11—C10—C9	178.8 (2)
C7—C6—N2—C5	33.7 (4)	C6—C11—C10—C9	0.2 (4)
C11—C6—N2—C5	−150.8 (2)	C8—C9—C10—C11	0.1 (4)
C4—S1—C1—C2	−0.4 (2)	C5—C4—C3—C2	−179.0 (2)
C4—S1—C1—N1	179.1 (2)	S1—C4—C3—C2	0.2 (3)
C6—C7—C8—C9	−1.2 (4)	N1—C1—C2—C3	−178.9 (2)
C2—C1—N1—O1	−2.5 (4)	S1—C1—C2—C3	0.6 (3)
S1—C1—N1—O1	178.03 (18)	C4—C3—C2—C1	−0.5 (3)
C2—C1—N1—O2	177.5 (2)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C6–C11 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg2ⁱ	0.93	2.77	3.605 (3)	149

Symmetry code: (i) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₃S
M_r	262.28
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	6.6825 (6), 7.7926 (5), 23.7180 (12)
V (Å³)	1235.09 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.59 × 0.39 × 0.05

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.974, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	5645, 2599, 1799
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.069, 0.93
No. of reflections	2599
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.21
Absolute structure	Flack (1983), 1067 Friedel pairs
Absolute structure parameter	−0.04 (8)

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C6–C11 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg2ⁱ	0.93	2.77	3.605 (3)	149

Symmetry code: (i) x−1/2, −y+1/2, −z.

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

References

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o393

doi:10.1107/S160053681200044X

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