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The title compound, C12H11N3OS, was synthesized by the reaction of 2-pyridine­carbonyl­hydrazide with 2-acetyl­thio­phene in ethanol. In the mol­ecule, the dihedral angle between the pyridine and thio­phene rings is 24.4 (3)°. In the crystal structure, zigzag chains are formed along the b axis by weak inter­molecular C—H...N inter­actions. These chains are, in turn, further assembled into a two-dimensional supra­molecular structure through weak inter­molecular C—H...O and N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049811/lh2521sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049811/lh2521Isup2.hkl
Contains datablock I

CCDC reference: 656252

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.046
  • wR factor = 0.154
  • Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 8 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C7 PLAT414_ALERT_2_C Short Intra D-H..H-X H1 .. H7A .. 1.90 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H1 .. O1 .. 2.69 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

In recent years, much attention has been devoted to multinuclear complex systems with aroylhydrazone ligands due to their interesting structural and magnetic properties (Matthews et al., 1999; Bernhardt et al. 2006). Investigation of the crystal structures of aroylhydrazone ligands may provide useful information concerning their coordination potential. In the present study, we report the synthesis and structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The X-ray single-crystal analysis reveals that the compound is non-planar and the dihedral angle between the two aromatic rings is 24.4 (3)°. The molecule displays a trans configuration with respect to the C—N double bond. All bond lengths show normal values (Allen et al., 1987; Pan et al., 2005). The C8—N2 bond length of 1.285 (7) Å conforms to the value for a double bond. Bond lengths C1—O1 and C1—N2 are 1.215 (6) Å and 1.335 (7) Å, respectively, indicating that the molecule exists in the keto form.

Atoms C11 of the thiophene group in one molecule and atoms N2 of the hydrazide group in adjacent molecule act as acceptor and donor to form the C—H···N weak interactions (Table 2). The occurrence of C—H···N weak interactions results in the formation of infinite zigzag chains along [010]. The chains are further assembled into a two-dimensional supramolecular structure through intermolecular C—H···O weak interactions and N—H···O hydrogen bonds (Fig. 2).

Related literature top

For the crystal structures of metal complexes with related aroylhydrazone derivatives, see: Matthews et al. (1999); Bernhardt et al. (2006). For bond lengths in molecules related to the title compound, see: Allen et al. (1987); Pan & Yang (2005).

Experimental top

Pyridine-2-carboxylic acid hydrazide (1.37 g, 10 mmol) was dissolved in anhydrous ethanol (30 ml), and 2-acetylthiophene (1.26 g, 10 mmol) was added. The reaction mixture was refluxed for 6 h to give a clear yellow solution. Light-yellow crystals suitable for X-ray diffraction were obtained at the bottom of the vessel after standing at room temperature in air for 8 d (yield 83%, m.p. 443–444 K). Analysis calculated for C12H11N3OS: C 58.76, H 4.52, N 17.13%; found: C 58.74, H 4.58, N 17.10%.

Refinement top

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H 0.96 Å (methyl) [Uiso(H) = 1.5Ueq(C)] and N—H 0.86 C—H 0.93 Å [Uiso(H) = 1.2Ueq(C, N)].

Structure description top

In recent years, much attention has been devoted to multinuclear complex systems with aroylhydrazone ligands due to their interesting structural and magnetic properties (Matthews et al., 1999; Bernhardt et al. 2006). Investigation of the crystal structures of aroylhydrazone ligands may provide useful information concerning their coordination potential. In the present study, we report the synthesis and structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The X-ray single-crystal analysis reveals that the compound is non-planar and the dihedral angle between the two aromatic rings is 24.4 (3)°. The molecule displays a trans configuration with respect to the C—N double bond. All bond lengths show normal values (Allen et al., 1987; Pan et al., 2005). The C8—N2 bond length of 1.285 (7) Å conforms to the value for a double bond. Bond lengths C1—O1 and C1—N2 are 1.215 (6) Å and 1.335 (7) Å, respectively, indicating that the molecule exists in the keto form.

Atoms C11 of the thiophene group in one molecule and atoms N2 of the hydrazide group in adjacent molecule act as acceptor and donor to form the C—H···N weak interactions (Table 2). The occurrence of C—H···N weak interactions results in the formation of infinite zigzag chains along [010]. The chains are further assembled into a two-dimensional supramolecular structure through intermolecular C—H···O weak interactions and N—H···O hydrogen bonds (Fig. 2).

For the crystal structures of metal complexes with related aroylhydrazone derivatives, see: Matthews et al. (1999); Bernhardt et al. (2006). For bond lengths in molecules related to the title compound, see: Allen et al. (1987); Pan & Yang (2005).

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, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of the title compound. Hydrogen bonds are shown as dashed lines.
N'-[1-(2-Thienyl)ethylidene]pyridine-2-carbohydrazide top
Crystal data top
C12H11N3OSF(000) = 512
Mr = 245.30Dx = 1.377 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2156 reflections
a = 12.162 (2) Åθ = 2.7–26.2°
b = 9.8259 (16) ŵ = 0.26 mm1
c = 10.2461 (17) ÅT = 298 K
β = 104.857 (2)°Block, light-yellow
V = 1183.5 (4) Å30.56 × 0.50 × 0.22 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
2088 independent reflections
Radiation source: fine-focus sealed tube1531 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1314
Tmin = 0.868, Tmax = 0.945k = 116
5755 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0845P)2 + 0.601P]
where P = (Fo2 + 2Fc2)/3
2088 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.32 e Å3
1 restraintΔρmin = 0.26 e Å3
Crystal data top
C12H11N3OSV = 1183.5 (4) Å3
Mr = 245.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.162 (2) ŵ = 0.26 mm1
b = 9.8259 (16) ÅT = 298 K
c = 10.2461 (17) Å0.56 × 0.50 × 0.22 mm
β = 104.857 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
2088 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1531 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 0.945Rint = 0.025
5755 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0461 restraint
wR(F2) = 0.154H-atom parameters constrained
S = 1.01Δρmax = 0.32 e Å3
2088 reflectionsΔρmin = 0.26 e Å3
154 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
xyzUiso*/Ueq
N10.1445 (4)0.8579 (5)0.0924 (5)0.0484 (12)
H10.11330.87290.00840.058*
N20.2426 (4)0.9265 (4)0.1575 (4)0.0447 (11)
N30.0534 (4)0.7579 (5)0.0438 (4)0.0482 (12)
O10.1393 (3)0.7400 (4)0.2790 (4)0.0579 (12)
S10.43434 (14)1.0654 (2)0.33637 (15)0.0677 (7)
C10.0987 (4)0.7684 (6)0.1611 (5)0.0431 (13)
C20.0087 (4)0.7049 (5)0.0788 (5)0.0416 (12)
C30.0575 (5)0.5980 (6)0.1313 (6)0.0512 (15)
H30.02410.56420.21710.061*
C40.1572 (5)0.5424 (7)0.0530 (6)0.0585 (16)
H40.19220.47010.08500.070*
C50.2034 (5)0.5957 (7)0.0723 (6)0.0595 (17)
H50.27050.56040.12690.071*
C60.1494 (5)0.7020 (7)0.1162 (6)0.0568 (16)
H60.18170.73720.20170.068*
C70.2513 (5)1.0330 (7)0.0622 (6)0.0583 (16)
H7A0.18280.98300.10040.087*
H7B0.30931.00580.10510.087*
H7C0.23681.12860.07610.087*
C80.2906 (4)1.0040 (5)0.0875 (5)0.0414 (12)
C90.3943 (4)1.0717 (5)0.1632 (5)0.0426 (13)
C100.4717 (5)1.1431 (7)0.1159 (6)0.0607 (17)
H100.46501.15850.02470.073*
C110.5637 (5)1.1916 (7)0.2204 (7)0.0663 (18)
H110.62421.24130.20490.080*
C120.5543 (5)1.1585 (7)0.3430 (7)0.0596 (17)
H120.60681.18310.42270.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.040 (2)0.055 (3)0.044 (2)0.009 (2)0.0010 (19)0.006 (2)
N20.035 (2)0.048 (3)0.046 (3)0.004 (2)0.0006 (19)0.003 (2)
N30.041 (3)0.054 (3)0.047 (3)0.004 (2)0.007 (2)0.000 (2)
O10.052 (2)0.070 (3)0.046 (2)0.008 (2)0.0029 (18)0.010 (2)
S10.0572 (11)0.0936 (14)0.0457 (10)0.0204 (9)0.0013 (7)0.0024 (8)
C10.037 (3)0.045 (3)0.046 (3)0.003 (2)0.008 (2)0.001 (2)
C20.039 (3)0.042 (3)0.045 (3)0.002 (2)0.012 (2)0.002 (2)
C30.048 (3)0.057 (4)0.049 (3)0.003 (3)0.013 (3)0.003 (3)
C40.054 (4)0.062 (4)0.062 (4)0.016 (3)0.021 (3)0.002 (3)
C50.048 (3)0.073 (4)0.056 (4)0.018 (3)0.011 (3)0.013 (3)
C60.050 (3)0.068 (4)0.048 (3)0.004 (3)0.004 (3)0.002 (3)
C70.061 (4)0.064 (4)0.044 (3)0.010 (3)0.003 (3)0.001 (3)
C80.040 (3)0.040 (3)0.041 (3)0.002 (2)0.005 (2)0.001 (2)
C90.041 (3)0.038 (3)0.046 (3)0.001 (2)0.006 (2)0.001 (2)
C100.060 (4)0.063 (4)0.057 (4)0.018 (3)0.012 (3)0.002 (3)
C110.054 (4)0.062 (4)0.081 (5)0.019 (3)0.014 (3)0.010 (4)
C120.043 (3)0.066 (4)0.062 (4)0.007 (3)0.001 (3)0.015 (3)
Geometric parameters (Å, º) top
N1—C11.335 (7)C5—C61.370 (9)
N1—N21.384 (6)C5—H50.9300
N1—H10.8600C6—H60.9300
N2—C81.285 (7)C7—C81.512 (7)
N3—C61.331 (7)C7—H7A0.9600
N3—C21.339 (7)C7—H7B0.9600
O1—C11.215 (6)C7—H7C0.9600
S1—C121.709 (6)C8—C91.460 (7)
S1—C91.716 (6)C9—C101.359 (8)
C1—C21.497 (7)C10—C111.419 (9)
C2—C31.382 (8)C10—H100.9300
C3—C41.384 (8)C11—C121.330 (9)
C3—H30.9300C11—H110.9300
C4—C51.367 (9)C12—H120.9300
C4—H40.9300
C1—N1—N2119.5 (4)C5—C6—H6118.1
C1—N1—H1120.2C8—C7—H7A109.5
N2—N1—H1120.2C8—C7—H7B109.5
C8—N2—N1118.6 (4)H7A—C7—H7B109.5
C6—N3—C2116.7 (5)C8—C7—H7C109.5
C12—S1—C992.0 (3)H7A—C7—H7C109.5
O1—C1—N1123.9 (5)H7B—C7—H7C109.5
O1—C1—C2122.6 (5)N2—C8—C9115.3 (5)
N1—C1—C2113.6 (5)N2—C8—C7127.4 (5)
N3—C2—C3123.3 (5)C9—C8—C7117.4 (5)
N3—C2—C1116.9 (5)C10—C9—C8128.9 (5)
C3—C2—C1119.8 (5)C10—C9—S1110.4 (4)
C2—C3—C4118.3 (6)C8—C9—S1120.7 (4)
C2—C3—H3120.8C9—C10—C11112.9 (6)
C4—C3—H3120.8C9—C10—H10123.5
C5—C4—C3118.8 (6)C11—C10—H10123.5
C5—C4—H4120.6C12—C11—C10112.8 (6)
C3—C4—H4120.6C12—C11—H11123.6
C4—C5—C6119.0 (6)C10—C11—H11123.6
C4—C5—H5120.5C11—C12—S1111.9 (5)
C6—C5—H5120.5C11—C12—H12124.1
N3—C6—C5123.9 (6)S1—C12—H12124.1
N3—C6—H6118.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···O1i0.962.503.250 (7)135
N1—H1···O1i0.862.693.337 (6)133
C11—H11···N2ii0.932.603.306 (8)133
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H11N3OS
Mr245.30
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)12.162 (2), 9.8259 (16), 10.2461 (17)
β (°) 104.857 (2)
V3)1183.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.26
Crystal size (mm)0.56 × 0.50 × 0.22
Data collection
DiffractometerSiemens SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.868, 0.945
No. of measured, independent and
observed [I > 2σ(I)] reflections
5755, 2088, 1531
Rint0.025
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.154, 1.01
No. of reflections2088
No. of parameters154
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.26

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7A···O1i0.962.503.250 (7)134.5
N1—H1···O1i0.862.693.337 (6)133.1
C11—H11···N2ii0.932.603.306 (8)133.2
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y+1/2, z+1/2.
 

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