organic compounds
2-Amino-5-nitro-N-[(E)-thiophen-2-ylmethylidene]aniline
aDepartment of Chemistry, State University of New York-College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA
*Correspondence e-mail: geiger@geneseo.edu
In the title molecule, C11H9N3O2S, the thiophene and benzene rings form a dihedral angle of 17.68 (9)°. The thiophene S atom and the imine N atom are syn with respect to each other. In the crystal, N—H⋯O and N—H⋯N hydrogen bonds connect molecules, forming a two-dimensional network parallel to (10-1).
Related literature
For similar structures, see: Asiri et al. (2012a,b); Prasath et al. (2010). For a discussion of the use of Schiff base compounds containing thiophene in fluorescent chemosensors, see: Chen et al. (2012). For a review of the biological use of 2-thiophenes, see Kleemann et al. (2006). For a from a related study on thiophene-substituted benzimidazoles, see: Geiger et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2010); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2004) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812037464/lh5523sup1.cif
contains datablocks I, global. DOI:Supporting information file. DOI: https://doi.org/10.1107/S1600536812037464/lh5523Isup2.mol
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037464/lh5523Isup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812037464/lh5523Isup4.cml
0.500 g (3.26 mmol) 4-Nitro-1,2-diaminobenzene and 1.3 ml (6.5 mmole) 2-thiophenecarboxaldehyde were stirred in 130 ml ethanol under nitrogen for 3 days. After removal of the solvent via rotory evaporation, the crude product was recrystallized from equal volumes of dichloromethane and diethylether. A golden solid was obtained in 70% yield. 1H NMR spectrum (CDCl3, 400 MHz, p.p.m.): 8.76 (1H, s), 7.99 (2H, m), 7.55 (2H, m), 7.17 (1H, t), 6.70 (1H, d), 5.00 (2H, bs).
Single crystals were obtained via vapor diffusion of hexanes into a concentrated 1-propanol solution of the title compound.
The amine hydrogen atoms (HA, HB) and the imine hydrogen atom (H7) were refined isotropically. All other hydrogen atoms were refined using a riding model (AFIX 43). The hydrogen atom thermal parameters were set using the approximation Uiso = 1.2Ueq(C).
Besides their pharmacolgical importance (Kleemann et al., 2006), thiophene-containing compounds are of interest because of there potential use in chemical sensors (Chen et al., 2012). The title compound was isolated during our continuing studies of thiophene-substituted benzimidazoles (Geiger et al., 2012).
The title compound exhibits syn geometry about the imine group. A perspective view of the compound is shown in Figure 1. The thiophene and benzene rings are slightly tilted with an interplanar angle of 17.58 (9)°. The imine group displays a torsional angle (C2-N2-C7-C8) of 178.5 (2)°. The plane of the nitro group is 3.6 (2)° out of the benzene ring mean plane.
A two dimensional hydrogen-bonded network (Fig. 2) emanating from the amino group and extending to a nitro oxygen atom and an imine nitrogen atom connects symmetry related molecules parallel to (101).
For similar structures, see: Asiri et al. (2012a,b); Prasath et al. (2010). For a discussion of the use of Schiff base compounds containing thiophene in fluorescent chemosensors, see: Chen et al. (2012). For a review of the biological use of 2-thiophenes, see Kleemann et al. (2006). For a
from a related study on thiophene-substituted benzimidazoles, see: Geiger et al. (2012).Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2004) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).C11H9N3O2S | F(000) = 1024 |
Mr = 247.27 | Dx = 1.522 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2950 reflections |
a = 24.335 (4) Å | θ = 2.3–25.0° |
b = 7.2084 (10) Å | µ = 0.29 mm−1 |
c = 16.932 (3) Å | T = 200 K |
β = 133.396 (10)° | Plate, orange |
V = 2158.3 (6) Å3 | 0.60 × 0.30 × 0.20 mm |
Z = 8 |
Bruker SMART X2S benchtop diffractometer | 1923 independent reflections |
Radiation source: XOS X-beam microfocus source | 1619 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.072 |
ω scans | θmax = 25.1°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −25→28 |
Tmin = 0.844, Tmax = 0.944 | k = −8→8 |
6460 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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0862P)2 + 0.1606P] where P = (Fo2 + 2Fc2)/3 |
1923 reflections | (Δ/σ)max < 0.001 |
166 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.46 e Å−3 |
C11H9N3O2S | V = 2158.3 (6) Å3 |
Mr = 247.27 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.335 (4) Å | µ = 0.29 mm−1 |
b = 7.2084 (10) Å | T = 200 K |
c = 16.932 (3) Å | 0.60 × 0.30 × 0.20 mm |
β = 133.396 (10)° |
Bruker SMART X2S benchtop diffractometer | 1923 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1619 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.944 | Rint = 0.072 |
6460 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.45 e Å−3 |
1923 reflections | Δρmin = −0.46 e Å−3 |
166 parameters |
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 | ||
S1 | 0.37474 (3) | −0.02144 (9) | 0.15352 (4) | 0.0390 (3) | |
O1 | −0.11073 (9) | 0.1684 (3) | −0.18166 (15) | 0.0536 (5) | |
O2 | −0.06193 (9) | 0.0037 (3) | −0.22717 (13) | 0.0485 (5) | |
N1 | 0.23171 (10) | 0.3033 (3) | 0.22589 (14) | 0.0317 (4) | |
HA | 0.2348 (12) | 0.384 (3) | 0.268 (2) | 0.033 (6)* | |
HB | 0.2669 (13) | 0.292 (3) | 0.230 (2) | 0.040 (7)* | |
N2 | 0.22136 (9) | 0.0875 (2) | 0.08347 (13) | 0.0246 (4) | |
N3 | −0.05550 (10) | 0.1071 (3) | −0.16331 (15) | 0.0356 (5) | |
C1 | 0.16213 (10) | 0.2554 (3) | 0.13152 (15) | 0.0227 (4) | |
C2 | 0.15340 (11) | 0.1461 (3) | 0.05347 (15) | 0.0225 (4) | |
C3 | 0.08196 (11) | 0.0985 (3) | −0.04247 (15) | 0.0250 (5) | |
H3 | 0.0758 | 0.0245 | −0.0945 | 0.030* | |
C4 | 0.01887 (11) | 0.1588 (3) | −0.06301 (16) | 0.0268 (5) | |
C5 | 0.02641 (12) | 0.2658 (3) | 0.01241 (18) | 0.0318 (5) | |
H5 | −0.0171 | 0.3059 | −0.0024 | 0.038* | |
C6 | 0.09727 (12) | 0.3126 (3) | 0.10818 (17) | 0.0305 (5) | |
H6 | 0.1025 | 0.3853 | 0.1598 | 0.037* | |
C7 | 0.21931 (11) | 0.0503 (3) | 0.00748 (16) | 0.0243 (4) | |
H7 | 0.1755 (11) | 0.058 (3) | −0.0645 (17) | 0.020 (5)* | |
C8 | 0.28411 (11) | −0.0148 (3) | 0.02707 (16) | 0.0242 (5) | |
C9 | 0.28193 (11) | −0.0775 (3) | −0.05083 (16) | 0.0285 (5) | |
H9 | 0.2371 | −0.0815 | −0.1260 | 0.034* | |
C10 | 0.35331 (12) | −0.1360 (3) | −0.00832 (17) | 0.0304 (5) | |
H10 | 0.3616 | −0.1855 | −0.0514 | 0.037* | |
C11 | 0.40851 (13) | −0.1137 (3) | 0.10053 (18) | 0.0377 (6) | |
H11 | 0.4600 | −0.1455 | 0.1427 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0295 (4) | 0.0638 (5) | 0.0252 (4) | 0.0090 (2) | 0.0193 (3) | 0.0003 (2) |
O1 | 0.0246 (9) | 0.0738 (13) | 0.0535 (11) | 0.0082 (8) | 0.0235 (8) | 0.0051 (9) |
O2 | 0.0351 (10) | 0.0698 (12) | 0.0314 (9) | −0.0101 (8) | 0.0193 (8) | −0.0121 (8) |
N1 | 0.0313 (10) | 0.0408 (11) | 0.0265 (9) | −0.0039 (8) | 0.0213 (9) | −0.0060 (8) |
N2 | 0.0262 (9) | 0.0252 (9) | 0.0284 (8) | 0.0010 (7) | 0.0210 (8) | −0.0007 (7) |
N3 | 0.0254 (10) | 0.0443 (11) | 0.0340 (10) | 0.0012 (8) | 0.0192 (8) | 0.0081 (8) |
C1 | 0.0269 (10) | 0.0232 (9) | 0.0238 (9) | 0.0013 (8) | 0.0196 (8) | 0.0035 (8) |
C2 | 0.0262 (10) | 0.0225 (10) | 0.0253 (10) | 0.0023 (8) | 0.0202 (9) | 0.0041 (8) |
C3 | 0.0280 (11) | 0.0266 (11) | 0.0255 (9) | −0.0004 (8) | 0.0204 (9) | −0.0007 (8) |
C4 | 0.0230 (10) | 0.0311 (11) | 0.0282 (10) | 0.0000 (8) | 0.0183 (9) | 0.0031 (8) |
C5 | 0.0315 (11) | 0.0356 (11) | 0.0413 (11) | 0.0036 (9) | 0.0301 (10) | 0.0046 (10) |
C6 | 0.0380 (12) | 0.0325 (11) | 0.0344 (11) | 0.0023 (9) | 0.0300 (10) | −0.0015 (9) |
C7 | 0.0277 (11) | 0.0238 (10) | 0.0256 (10) | 0.0012 (8) | 0.0199 (9) | 0.0037 (8) |
C8 | 0.0269 (11) | 0.0242 (10) | 0.0288 (10) | 0.0023 (8) | 0.0220 (10) | 0.0043 (8) |
C9 | 0.0335 (11) | 0.0312 (11) | 0.0286 (10) | −0.0019 (9) | 0.0243 (10) | 0.0016 (9) |
C10 | 0.0371 (12) | 0.0322 (11) | 0.0377 (11) | 0.0039 (9) | 0.0317 (11) | 0.0020 (9) |
C11 | 0.0304 (12) | 0.0523 (14) | 0.0373 (11) | 0.0091 (10) | 0.0259 (10) | 0.0046 (10) |
S1—C11 | 1.713 (2) | C3—H3 | 0.9500 |
S1—C8 | 1.721 (2) | C4—C5 | 1.392 (3) |
O1—N3 | 1.235 (2) | C5—C6 | 1.369 (3) |
O2—N3 | 1.232 (2) | C5—H5 | 0.9500 |
N1—C1 | 1.350 (3) | C6—H6 | 0.9500 |
N1—HA | 0.88 (2) | C7—C8 | 1.449 (3) |
N1—HB | 0.81 (2) | C7—H7 | 0.92 (2) |
N2—C7 | 1.281 (3) | C8—C9 | 1.360 (3) |
N2—C2 | 1.420 (2) | C9—C10 | 1.413 (3) |
N3—C4 | 1.440 (3) | C9—H9 | 0.9500 |
C1—C6 | 1.400 (3) | C10—C11 | 1.351 (3) |
C1—C2 | 1.424 (3) | C10—H10 | 0.9500 |
C2—C3 | 1.378 (3) | C11—H11 | 0.9500 |
C3—C4 | 1.391 (2) | ||
C11—S1—C8 | 91.44 (10) | C6—C5—H5 | 120.4 |
C1—N1—HA | 117.8 (14) | C4—C5—H5 | 120.4 |
C1—N1—HB | 118.2 (18) | C5—C6—C1 | 121.34 (18) |
HA—N1—HB | 119 (2) | C5—C6—H6 | 119.3 |
C7—N2—C2 | 118.08 (16) | C1—C6—H6 | 119.3 |
O2—N3—O1 | 122.40 (19) | N2—C7—C8 | 123.55 (18) |
O2—N3—C4 | 119.38 (17) | N2—C7—H7 | 122.0 (12) |
O1—N3—C4 | 118.23 (19) | C8—C7—H7 | 114.4 (12) |
N1—C1—C6 | 120.86 (18) | C9—C8—C7 | 125.06 (19) |
N1—C1—C2 | 120.42 (17) | C9—C8—S1 | 111.09 (15) |
C6—C1—C2 | 118.72 (17) | C7—C8—S1 | 123.84 (15) |
C3—C2—N2 | 124.30 (16) | C8—C9—C10 | 112.96 (18) |
C3—C2—C1 | 119.68 (17) | C8—C9—H9 | 123.5 |
N2—C2—C1 | 115.98 (17) | C10—C9—H9 | 123.5 |
C2—C3—C4 | 119.93 (17) | C11—C10—C9 | 112.44 (18) |
C2—C3—H3 | 120.0 | C11—C10—H10 | 123.8 |
C4—C3—H3 | 120.0 | C9—C10—H10 | 123.8 |
C3—C4—C5 | 121.12 (18) | C10—C11—S1 | 112.05 (16) |
C3—C4—N3 | 119.41 (17) | C10—C11—H11 | 124.0 |
C5—C4—N3 | 119.47 (17) | S1—C11—H11 | 124.0 |
C6—C5—C4 | 119.21 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—HB···O1i | 0.81 (2) | 2.25 (2) | 2.991 (2) | 152 (2) |
N1—HA···N2ii | 0.88 (2) | 2.43 (3) | 3.295 (2) | 164.9 (19) |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H9N3O2S |
Mr | 247.27 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 200 |
a, b, c (Å) | 24.335 (4), 7.2084 (10), 16.932 (3) |
β (°) | 133.396 (10) |
V (Å3) | 2158.3 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.60 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART X2S benchtop |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.844, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6460, 1923, 1619 |
Rint | 0.072 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.138, 1.09 |
No. of reflections | 1923 |
No. of parameters | 166 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.45, −0.46 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XSHELL (Bruker, 2004) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—HB···O1i | 0.81 (2) | 2.25 (2) | 2.991 (2) | 152 (2) |
N1—HA···N2ii | 0.88 (2) | 2.43 (3) | 3.295 (2) | 164.9 (19) |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
Acknowledgements
This work was supported by a Congressionally directed grant from the US Department of Education (grant No. P116Z100020) for the X-ray diffractometer and a grant from the Geneseo Foundation.
References
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Besides their pharmacolgical importance (Kleemann et al., 2006), thiophene-containing compounds are of interest because of there potential use in chemical sensors (Chen et al., 2012). The title compound was isolated during our continuing studies of thiophene-substituted benzimidazoles (Geiger et al., 2012).
The title compound exhibits syn geometry about the imine group. A perspective view of the compound is shown in Figure 1. The thiophene and benzene rings are slightly tilted with an interplanar angle of 17.58 (9)°. The imine group displays a torsional angle (C2-N2-C7-C8) of 178.5 (2)°. The plane of the nitro group is 3.6 (2)° out of the benzene ring mean plane.
A two dimensional hydrogen-bonded network (Fig. 2) emanating from the amino group and extending to a nitro oxygen atom and an imine nitrogen atom connects symmetry related molecules parallel to (101).