Thio­phene-2-carbaldehyde 2,4-dinitro­phenyl­hydrazone

Yin, Z.; Qian, H.; Li, H.; Hu, J.; Zhang, C.

doi:10.1107/S1600536808038397

organic compounds

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Volume 64| Part 12| December 2008| Page o2421

doi:10.1107/S1600536808038397

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Thiophene-2-carbaldehyde 2,4-dinitrophenylhydrazone

Zhi-gang Yin,^a ^* Heng-yu Qian,^a He-ping Li,^b Jie Hu ^a and Chun-xia Zhang ^a

^aKey Laboratory of Surface and Interface Science of Henan, School of Materials and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China, and ^bDepartment of Materials and Chemical Engineering, Guiling University of Technology, People's Republic of China
^*Correspondence e-mail: yinck@263.net

(Received 13 November 2008; accepted 18 November 2008; online 22 November 2008)

In the approximately planar molecule of the title compound, C₁₁H₈N₄O₄S, the dihedral angle between the thiophene and benzene rings is 5.73 (10)°. In the crystal structure, bifurcated inter/intramolecular N—H⋯(O,O) hydrogen bonds are present. The intermolecular links lead to inversion dimers containing an R₂²(12) graph-set motif.

Related literature

For general background, see: Okabe et al. (1993 ). For graph-set notation, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₈N₄O₄S
M_r = 292.27
Monoclinic, P 2₁ /c
a = 4.8994 (17) Å
b = 9.520 (3) Å
c = 25.708 (8) Å
β = 92.71 (2)°
V = 1197.7 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 291 (2) K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.915, T_max = 0.929
11010 measured reflections
2285 independent reflections
1718 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.087
S = 1.02
2285 reflections
184 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯O1ⁱ	0.87 (2)	2.57 (2)	3.338 (2)	148.2 (19)
N3—H1⋯O1	0.87 (2)	2.01 (2)	2.630 (2)	127.4 (19)
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038397/dn2406sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038397/dn2406Isup2.hkl

checkCIF report

Comment top

2,4-Dinitrophenylhydrazine is a reagent which is widely used for condensation with aldehydes and ketones. Several phenylhydrazone derivatives have been shown to be potentially DNA-damaging and are mutagenic agents(Okabe et al. 1993). As part of our work, we have synthesized the title compound (I) and reported its cyrstal structure.

The title molecule is roughly planar. Indeed, the benzene and the thiophene rings are only slight twisted, making a dihedral angle of 5.73 (10)° (Fig. 1). The two nitro groups, O1/N1/O2 and O3/N2/O4 are coplanar with the benzene ring to which they are attached.

Intermolecular N-H···O hydrogen bonds link the molecule two by two around inversion center, building then a R₂²(12) graph set motif (Etter et al., 1990; Bernstein et al., 1995) if the intramolecular N-H···O hydrogen bonds are ignored (Table 1, Fig.2).

Related literature top

For general background, see: Okabe et al. (1993). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

2,4-dinitrophenylhydrazine(1 mmol, 0.198 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, thiophene-2-carbaldehyde (1 mmol 0.112 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in methanol, purple single crystals of (I) was obtained after 5 d.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. View showing the N-H···O hydrogen bonds buiding a R₂²(12) graph set motif. Hydrogen bonds are shown as dashed lines.

Thiophene-2-carbaldehyde 2,4-dinitrophenylhydrazone top

Crystal data top

C₁₁H₈N₄O₄S	F(000) = 600
M_r = 292.27	D_x = 1.621 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5391 reflections
a = 4.8994 (17) Å	θ = 2.3–27.4°
b = 9.520 (3) Å	µ = 0.29 mm⁻¹
c = 25.708 (8) Å	T = 291 K
β = 92.71 (2)°	Block, purple
V = 1197.7 (7) Å³	0.30 × 0.26 × 0.24 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2285 independent reflections
Radiation source: sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −6→5
T_min = 0.915, T_max = 0.929	k = −11→11
11010 measured reflections	l = −31→29

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
2285 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₁H₈N₄O₄S	V = 1197.7 (7) Å³
M_r = 292.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8994 (17) Å	µ = 0.29 mm⁻¹
b = 9.520 (3) Å	T = 291 K
c = 25.708 (8) Å	0.30 × 0.26 × 0.24 mm
β = 92.71 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2285 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1718 reflections with I > 2σ(I)
T_min = 0.915, T_max = 0.929	R_int = 0.047
11010 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.16 e Å⁻³
2285 reflections	Δρ_min = −0.19 e Å⁻³
184 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
C1	0.1154 (4)	0.2360 (2)	0.04553 (7)	0.0342 (4)
C2	−0.0759 (4)	0.1287 (2)	0.04720 (7)	0.0350 (4)
H2	−0.2010	0.1150	0.0193	0.042*
C3	−0.0801 (4)	0.04351 (18)	0.08984 (7)	0.0315 (4)
C4	0.1065 (4)	0.0673 (2)	0.13207 (7)	0.0383 (5)
H4	0.1048	0.0087	0.1610	0.046*
C5	0.2882 (4)	0.1738 (2)	0.13141 (7)	0.0350 (4)
H5	0.4096	0.1870	0.1599	0.042*
C6	0.2980 (4)	0.26512 (18)	0.08856 (7)	0.0291 (4)
C7	0.8165 (4)	0.49823 (19)	0.13079 (7)	0.0389 (5)
H7	0.7974	0.5614	0.1033	0.047*
C8	1.0163 (4)	0.52284 (19)	0.17283 (7)	0.0341 (4)
C9	1.1994 (5)	0.6353 (2)	0.17481 (8)	0.0418 (5)
H9	1.2066	0.7050	0.1496	0.050*
C10	1.3738 (5)	0.6289 (2)	0.22076 (9)	0.0465 (5)
H10	1.5107	0.6939	0.2290	0.056*
C11	1.3173 (5)	0.5174 (2)	0.25090 (8)	0.0522 (6)
H11	1.4113	0.4975	0.2823	0.063*
N1	0.0973 (4)	0.31477 (18)	0.00000 (6)	0.0394 (4)
N2	−0.2778 (4)	−0.06932 (17)	0.09065 (7)	0.0414 (4)
N3	0.4846 (4)	0.37052 (17)	0.08923 (6)	0.0378 (4)
H1	0.483 (5)	0.426 (2)	0.0624 (9)	0.045*
N4	0.6631 (3)	0.38663 (15)	0.13180 (6)	0.0321 (4)
O1	0.2484 (4)	0.41150 (16)	−0.00353 (6)	0.0545 (4)
O2	−0.0594 (3)	0.29004 (14)	−0.03604 (5)	0.0461 (4)
O3	−0.4272 (3)	−0.08987 (16)	0.05310 (6)	0.0526 (4)
O4	−0.2847 (3)	−0.13710 (15)	0.12986 (6)	0.0513 (4)
S1	1.05706 (12)	0.41736 (6)	0.22559 (2)	0.04762 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0302 (10)	0.0438 (10)	0.0277 (10)	−0.0016 (8)	−0.0096 (8)	−0.0034 (7)
C2	0.0330 (10)	0.0410 (10)	0.0303 (10)	−0.0007 (8)	−0.0046 (8)	−0.0039 (7)
C3	0.0326 (10)	0.0290 (8)	0.0325 (9)	−0.0001 (7)	−0.0024 (8)	−0.0025 (7)
C4	0.0414 (12)	0.0417 (10)	0.0314 (10)	0.0038 (8)	−0.0038 (9)	0.0075 (8)
C5	0.0259 (10)	0.0463 (10)	0.0323 (10)	0.0090 (8)	−0.0035 (8)	−0.0005 (8)
C6	0.0270 (9)	0.0339 (8)	0.0262 (9)	0.0002 (7)	−0.0004 (7)	−0.0062 (7)
C7	0.0510 (12)	0.0394 (10)	0.0257 (9)	−0.0026 (9)	−0.0057 (8)	−0.0013 (8)
C8	0.0316 (10)	0.0353 (9)	0.0349 (9)	−0.0023 (8)	−0.0025 (8)	−0.0079 (7)
C9	0.0473 (13)	0.0361 (9)	0.0412 (11)	−0.0042 (9)	−0.0073 (9)	−0.0059 (8)
C10	0.0387 (12)	0.0416 (10)	0.0581 (14)	−0.0045 (9)	−0.0105 (10)	−0.0220 (10)
C11	0.0629 (15)	0.0558 (13)	0.0357 (11)	0.0052 (11)	−0.0222 (11)	−0.0131 (9)
N1	0.0383 (10)	0.0452 (9)	0.0335 (9)	−0.0104 (8)	−0.0120 (8)	−0.0013 (7)
N2	0.0360 (10)	0.0421 (9)	0.0453 (10)	−0.0026 (7)	−0.0074 (8)	0.0047 (8)
N3	0.0387 (10)	0.0443 (9)	0.0290 (9)	−0.0077 (7)	−0.0126 (7)	−0.0001 (7)
N4	0.0345 (8)	0.0344 (8)	0.0266 (8)	−0.0003 (6)	−0.0087 (7)	−0.0040 (6)
O1	0.0659 (11)	0.0525 (9)	0.0435 (9)	−0.0225 (8)	−0.0163 (8)	0.0158 (7)
O2	0.0471 (9)	0.0505 (8)	0.0383 (8)	−0.0317 (7)	−0.0222 (7)	0.0182 (6)
O3	0.0488 (10)	0.0534 (9)	0.0537 (9)	−0.0260 (7)	−0.0185 (8)	−0.0002 (7)
O4	0.0566 (10)	0.0451 (8)	0.0519 (9)	−0.0169 (7)	−0.0008 (8)	0.0131 (7)
S1	0.0480 (3)	0.0553 (3)	0.0385 (3)	−0.0071 (2)	−0.0093 (2)	0.0040 (2)

Geometric parameters (Å, º) top

C1—C2	1.388 (3)	C8—C9	1.396 (3)
C1—N1	1.389 (2)	C8—S1	1.692 (2)
C1—C6	1.417 (2)	C9—C10	1.426 (3)
C2—C3	1.365 (3)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.351 (3)
C3—C4	1.404 (2)	C10—H10	0.9300
C3—N2	1.447 (2)	C11—S1	1.696 (2)
C4—C5	1.350 (3)	C11—H11	0.9300
C4—H4	0.9300	N1—O1	1.188 (2)
C5—C6	1.406 (3)	N1—O2	1.1983 (19)
C5—H5	0.9300	N2—O4	1.199 (2)
C6—N3	1.357 (2)	N2—O3	1.199 (2)
C7—N4	1.302 (2)	N3—N4	1.377 (2)
C7—C8	1.442 (2)	N3—H1	0.87 (2)
C7—H7	0.9300

C2—C1—N1	114.01 (15)	C9—C8—S1	112.01 (14)
C2—C1—C6	121.47 (17)	C7—C8—S1	123.66 (14)
N1—C1—C6	124.40 (17)	C8—C9—C10	110.86 (19)
C3—C2—C1	119.87 (17)	C8—C9—H9	124.6
C3—C2—H2	120.1	C10—C9—H9	124.6
C1—C2—H2	120.1	C11—C10—C9	112.19 (18)
C2—C3—C4	119.41 (17)	C11—C10—H10	123.9
C2—C3—N2	119.22 (15)	C9—C10—H10	123.9
C4—C3—N2	121.36 (16)	C10—C11—S1	113.08 (15)
C5—C4—C3	121.14 (18)	C10—C11—H11	123.5
C5—C4—H4	119.4	S1—C11—H11	123.5
C3—C4—H4	119.4	O1—N1—O2	118.16 (16)
C4—C5—C6	121.43 (17)	O1—N1—C1	117.89 (14)
C4—C5—H5	119.3	O2—N1—C1	123.94 (16)
C6—C5—H5	119.3	O4—N2—O3	123.26 (17)
N3—C6—C5	119.70 (15)	O4—N2—C3	117.21 (15)
N3—C6—C1	123.69 (17)	O3—N2—C3	119.53 (16)
C5—C6—C1	116.55 (17)	C6—N3—N4	119.65 (16)
N4—C7—C8	119.31 (16)	C6—N3—H1	117.6 (14)
N4—C7—H7	120.3	N4—N3—H1	122.8 (14)
C8—C7—H7	120.3	C7—N4—N3	114.87 (15)
C9—C8—C7	124.33 (18)	C8—S1—C11	91.85 (11)

N1—C1—C2—C3	180.00 (18)	C8—C9—C10—C11	−0.6 (3)
C6—C1—C2—C3	−3.8 (3)	C9—C10—C11—S1	0.1 (3)
C1—C2—C3—C4	1.3 (3)	C2—C1—N1—O1	177.51 (19)
C1—C2—C3—N2	−178.99 (18)	C6—C1—N1—O1	1.5 (3)
C2—C3—C4—C5	0.6 (3)	C2—C1—N1—O2	−3.3 (3)
N2—C3—C4—C5	−179.16 (18)	C6—C1—N1—O2	−179.4 (2)
C3—C4—C5—C6	0.1 (3)	C2—C3—N2—O4	−176.10 (19)
C4—C5—C6—N3	−179.66 (19)	C4—C3—N2—O4	3.6 (3)
C4—C5—C6—C1	−2.5 (3)	C2—C3—N2—O3	3.1 (3)
C2—C1—C6—N3	−178.60 (18)	C4—C3—N2—O3	−177.21 (19)
N1—C1—C6—N3	−2.8 (3)	C5—C6—N3—N4	0.2 (3)
C2—C1—C6—C5	4.3 (3)	C1—C6—N3—N4	−176.76 (17)
N1—C1—C6—C5	−179.88 (19)	C8—C7—N4—N3	−178.20 (17)
N4—C7—C8—C9	177.13 (19)	C6—N3—N4—C7	−173.88 (18)
N4—C7—C8—S1	−2.5 (3)	C9—C8—S1—C11	−0.66 (18)
C7—C8—C9—C10	−178.8 (2)	C7—C8—S1—C11	179.01 (19)
S1—C8—C9—C10	0.8 (2)	C10—C11—S1—C8	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1ⁱ	0.87 (2)	2.57 (2)	3.338 (2)	148.2 (19)
N3—H1···O1	0.87 (2)	2.01 (2)	2.630 (2)	127.4 (19)

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₈N₄O₄S
M_r	292.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	4.8994 (17), 9.520 (3), 25.708 (8)
β (°)	92.71 (2)
V (Å³)	1197.7 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.915, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	11010, 2285, 1718
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.087, 1.02
No. of reflections	2285
No. of parameters	184
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O1ⁱ	0.87 (2)	2.57 (2)	3.338 (2)	148.2 (19)
N3—H1···O1	0.87 (2)	2.01 (2)	2.630 (2)	127.4 (19)

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

The authors express their deep appreciation to the Startup Fund for PhDs of Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 2005001) and the Startup Fund for Masters of Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 000455).

References

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