N′-(4-Bromo­benzyl­idene)thio­phene-2-carbohydrazide

Jiang, J.-H.

doi:10.1107/S1600536810010603

organic compounds

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Volume 66| Part 4| April 2010| Page o922

doi:10.1107/S1600536810010603

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N′-(4-Bromobenzylidene)thiophene-2-carbohydrazide

Jin-He Jiang ^a ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: weifangjjh@126.com

(Received 19 March 2010; accepted 22 March 2010; online 27 March 2010)

In the title compound, C₁₂H₉BrN₂OS, the dihedral angle between the aromatic rings is 10.0 (2)°. In the crystal structure, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur, generating R₂²(8) loops. Weak aromatic π–π stacking [centroid–centroid separations = 3.825 (3) and 3.866 (3) Å] also occurs.

Related literature

For background to Schiff bases, see: Cimerman et al. (1997 ). For a related structure, see: Girgis (2006 ).

Experimental

Crystal data

C₁₂H₉BrN₂OS
M_r = 309.18
Monoclinic, P 2₁ /n
a = 6.0700 (12) Å
b = 16.983 (3) Å
c = 11.643 (2) Å
β = 94.85 (3)°
V = 1195.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.60 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
8238 measured reflections
2079 independent reflections
1614 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.163
S = 1.03
2079 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.00	2.828 (5)	161
Symmetry code: (i) -x-2, -y+1, -z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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 global, I. DOI: 10.1107/S1600536810010603/hb5368sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010603/hb5368Isup2.hkl

checkCIF report

Comment top

Schiff bases have received considerable attention in the literature. They are attractive from several points of view, such as the possibility of analytical application (Cimerman et al., 1997). As part of our search for new Schiff base compounds we synthesized the title compound (I), and describe its structure here.

The molcular structure of (I) is shown in Fig. 1. The C6—N2 bond length of 1.273 (3)Å is comparable with C—N double bond [1.281 (2) Å] reported (Girgis, 2006). In the crystal structure, molecules are linked by intermolecular N—H···O hydrogen bonds.

Related literature top

For background to Schiff bases, see: Cimerman et al. (1997). For a related structure, see: Girgis (2006).

Experimental top

A mixture of thiophene-2-carbohydrazide (0.05 mol), and 4-bromobenzaldehyde (0.05 mol) was stirred in refluxing ethanol (10 mL) for 4 h to afford the title compound (0.080 mol, yield 80%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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) showing 30% probability displacement ellipsoids.

N'-(4-Bromobenzylidene)thiophene-2-carbohydrazide top

Crystal data top

C₁₂H₉BrN₂OS	F(000) = 616
M_r = 309.18	D_x = 1.717 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1614 reflections
a = 6.0700 (12) Å	θ = 3.5–25.3°
b = 16.983 (3) Å	µ = 3.60 mm⁻¹
c = 11.643 (2) Å	T = 293 K
β = 94.85 (3)°	Block, colorless
V = 1195.9 (4) Å³	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1614 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.086
Graphite monochromator	θ_max = 25.3°, θ_min = 3.5°
ω scans	h = −6→7
8238 measured reflections	k = −19→19
2079 independent reflections	l = −13→13

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) = 0.163	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
2079 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

C₁₂H₉BrN₂OS	V = 1195.9 (4) Å³
M_r = 309.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.0700 (12) Å	µ = 3.60 mm⁻¹
b = 16.983 (3) Å	T = 293 K
c = 11.643 (2) Å	0.23 × 0.20 × 0.18 mm
β = 94.85 (3)°

Data collection top

Bruker SMART CCD diffractometer	1614 reflections with I > 2σ(I)
8238 measured reflections	R_int = 0.086
2079 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.03	Δρ_max = 0.75 e Å⁻³
2079 reflections	Δρ_min = −0.84 e Å⁻³
154 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br1	0.15443 (9)	0.87907 (3)	0.25958 (4)	0.0509 (3)
S1	−0.8655 (2)	0.61910 (7)	0.37457 (11)	0.0437 (4)
C6	−0.5332 (9)	0.6311 (2)	0.0959 (4)	0.0382 (11)
H6A	−0.5211	0.6061	0.0256	0.046*
N2	−0.6908 (7)	0.61169 (19)	0.1589 (3)	0.0390 (9)
C10	−0.0606 (8)	0.8041 (3)	0.2068 (4)	0.0396 (11)
N1	−0.8383 (6)	0.5559 (2)	0.1135 (3)	0.0390 (9)
H1A	−0.8193	0.5353	0.0475	0.047*
O1	−1.1473 (6)	0.4869 (2)	0.1217 (3)	0.0526 (9)
C5	−1.0117 (8)	0.5329 (2)	0.1702 (4)	0.0401 (11)
C1	−1.0383 (9)	0.6136 (3)	0.4824 (5)	0.0466 (13)
H1B	−1.0099	0.6383	0.5534	0.056*
C3	−1.2229 (8)	0.5388 (3)	0.3431 (4)	0.0431 (11)
H3A	−1.3366	0.5075	0.3099	0.052*
C11	−0.2387 (9)	0.7887 (3)	0.2738 (4)	0.0456 (12)
H11A	−0.2529	0.8163	0.3418	0.055*
C7	−0.3756 (7)	0.6916 (2)	0.1350 (4)	0.0363 (10)
C12	−0.3902 (8)	0.7326 (3)	0.2374 (4)	0.0449 (12)
H12A	−0.5061	0.7217	0.2822	0.054*
C4	−1.0404 (8)	0.5594 (2)	0.2876 (4)	0.0381 (10)
C9	−0.0451 (8)	0.7655 (2)	0.1054 (4)	0.0430 (11)
H9A	0.0705	0.7767	0.0604	0.052*
C8	−0.2019 (9)	0.7093 (3)	0.0693 (4)	0.0445 (12)
H8A	−0.1903	0.6832	−0.0001	0.053*
C2	−1.2204 (8)	0.5698 (2)	0.4544 (4)	0.0433 (11)
H2B	−1.3312	0.5612	0.5034	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0496 (5)	0.0514 (4)	0.0511 (5)	−0.01021 (19)	0.0003 (3)	0.00256 (19)
S1	0.0465 (8)	0.0495 (8)	0.0352 (8)	−0.0095 (5)	0.0039 (6)	−0.0090 (5)
C6	0.049 (3)	0.036 (2)	0.029 (3)	0.002 (2)	0.002 (2)	0.0009 (17)
N2	0.046 (3)	0.0360 (19)	0.034 (2)	−0.0016 (16)	−0.0017 (18)	−0.0028 (15)
C10	0.042 (3)	0.038 (2)	0.039 (3)	0.0005 (19)	0.002 (2)	0.0079 (18)
N1	0.041 (2)	0.040 (2)	0.036 (2)	−0.0064 (17)	0.0026 (17)	−0.0082 (15)
O1	0.060 (3)	0.055 (2)	0.042 (2)	−0.0194 (17)	0.0048 (17)	−0.0114 (15)
C5	0.047 (3)	0.034 (2)	0.039 (3)	−0.006 (2)	−0.001 (2)	−0.0020 (18)
C1	0.050 (3)	0.055 (3)	0.035 (3)	0.003 (2)	0.007 (2)	−0.009 (2)
C3	0.044 (3)	0.046 (3)	0.039 (3)	−0.010 (2)	0.006 (2)	−0.005 (2)
C11	0.051 (3)	0.049 (3)	0.037 (3)	−0.008 (2)	0.009 (2)	−0.008 (2)
C7	0.036 (3)	0.038 (2)	0.035 (3)	0.0043 (19)	0.0031 (19)	0.0085 (18)
C12	0.037 (3)	0.051 (3)	0.048 (3)	−0.007 (2)	0.012 (2)	−0.004 (2)
C4	0.048 (3)	0.033 (2)	0.033 (3)	0.0037 (19)	−0.002 (2)	−0.0031 (16)
C9	0.042 (3)	0.040 (2)	0.048 (3)	0.002 (2)	0.012 (2)	0.005 (2)
C8	0.058 (3)	0.041 (2)	0.036 (3)	0.000 (2)	0.010 (2)	−0.0029 (19)
C2	0.040 (3)	0.049 (3)	0.043 (3)	−0.001 (2)	0.013 (2)	−0.004 (2)

Geometric parameters (Å, º) top

Br1—C10	1.889 (5)	C1—H1B	0.9300
S1—C1	1.705 (5)	C3—C4	1.374 (7)
S1—C4	1.732 (5)	C3—C2	1.397 (6)
C6—N2	1.296 (6)	C3—H3A	0.9300
C6—C7	1.450 (7)	C11—C12	1.366 (7)
C6—H6A	0.9300	C11—H11A	0.9300
N2—N1	1.378 (5)	C7—C8	1.387 (6)
C10—C9	1.360 (6)	C7—C12	1.391 (6)
C10—C11	1.410 (7)	C12—H12A	0.9300
N1—C5	1.347 (6)	C9—C8	1.387 (7)
N1—H1A	0.8600	C9—H9A	0.9300
O1—C5	1.236 (5)	C8—H8A	0.9300
C5—C4	1.464 (6)	C2—H2B	0.9300
C1—C2	1.349 (7)

C1—S1—C4	90.8 (2)	C12—C11—H11A	120.5
N2—C6—C7	120.1 (4)	C10—C11—H11A	120.5
N2—C6—H6A	120.0	C8—C7—C12	118.0 (4)
C7—C6—H6A	120.0	C8—C7—C6	119.6 (4)
C6—N2—N1	116.4 (4)	C12—C7—C6	122.4 (4)
C9—C10—C11	120.2 (5)	C11—C12—C7	121.8 (4)
C9—C10—Br1	120.7 (4)	C11—C12—H12A	119.1
C11—C10—Br1	119.1 (4)	C7—C12—H12A	119.1
C5—N1—N2	121.4 (4)	C3—C4—C5	121.7 (4)
C5—N1—H1A	119.3	C3—C4—S1	110.6 (3)
N2—N1—H1A	119.3	C5—C4—S1	127.7 (4)
O1—C5—N1	118.5 (4)	C10—C9—C8	119.9 (4)
O1—C5—C4	119.6 (4)	C10—C9—H9A	120.1
N1—C5—C4	121.9 (4)	C8—C9—H9A	120.1
C2—C1—S1	113.3 (4)	C7—C8—C9	121.1 (4)
C2—C1—H1B	123.4	C7—C8—H8A	119.4
S1—C1—H1B	123.4	C9—C8—H8A	119.4
C4—C3—C2	113.2 (4)	C1—C2—C3	112.1 (4)
C4—C3—H3A	123.4	C1—C2—H2B	124.0
C2—C3—H3A	123.4	C3—C2—H2B	124.0
C12—C11—C10	119.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.00	2.828 (5)	161

Symmetry code: (i) −x−2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₉BrN₂OS
M_r	309.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.0700 (12), 16.983 (3), 11.643 (2)
β (°)	94.85 (3)
V (Å³)	1195.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.60
Crystal size (mm)	0.23 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8238, 2079, 1614
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.163, 1.03
No. of reflections	2079
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.84

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
N1—H1A···O1ⁱ	0.86	2.00	2.828 (5)	161

Symmetry code: (i) −x−2, −y+1, −z.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153. CrossRef CAS Web of Science Google Scholar
Girgis, A. S. (2006). J. Chem. Res. pp. 81–85. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o922

doi:10.1107/S1600536810010603

Open

access