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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 4| April 2008| Page o719
doi:10.1107/S1600536808004960

N′-(3-Thienylmethyl­ene)pyridine-2-carbohydrazide

Haojin Cheng,a Brandon Djukic,a Laura E. Harrington,b James F. Brittenb and Martin T. Lemairea*

aDepartment of Chemistry, Brock University, 500 Glenridge Avenue, St Catharines, Ontario, Canada L2S 3A1, and bMcMaster University, Department of Chemistry, 1280 Main Street W., Hamilton, Ontario, Canada L8S 4M1
*Correspondence e-mail: mlemaire@brocku.ca

(Received 16 January 2008; accepted 20 February 2008; online 14 March 2008)

The title compound, C11H9N3OS, was prepared to investigate the coordination chemistry of thio­phene-containing ligands as precursors to inter­esting metallopolymers. The mol­ecule is nearly planar. The angle between the thio­phene and pyridine rings is 8.63 (4)° and features the expected trans configuration about the imine bond. The structure is stabilized by a weak inter­molecular N—H⋯O hydrogen bond. The distance between centroids of adjacent thio­phene rings [3.67 (8) Å] suggests the presence of π–π inter­actions.

Related literature

The preparation and coordination chemistry of a similar compound containing a 2-substituted thio­phene were reported previously by El-Motaleb et al. (2005[El-Motaleb, A., Ramadan, M. & Issa, R. M. (2005). Transition Met. Chem. 30, 471-480.]); however, no structural details were provided. For related literature and structures of other mol­ecules containing the pyridine-2-carbonohydrazide system, see: Klingele & Brooker (2004[Klingele, M. H. & Brooker, S. (2004). Eur. J. Org. Chem. pp. 3422-3434.]); Xie et al. (2006[Xie, Y.-Q., Sheng, L.-Q., Zhu, W. & Shao, S.-C. (2006). Acta Cryst. E62, o26-o27.]); Zhang et al. (2006[Zhang, J., Ma, C.-A., Song, Q.-B. & Tiekink, E. R. T. (2006). Acta Cryst. E62, o2644-o2645.]).

[Scheme 1]

Experimental

Crystal data

  • C11H9N3OS

  • Mr = 231.27

  • Monoclinic, P 21 /c

  • a = 11.6817 (3) Å

  • b = 9.1454 (3) Å

  • c = 10.0890 (3) Å

  • β = 103.230 (1)°

  • V = 1049.24 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.29 mm−1

  • T = 173 (2) K

  • 0.40 × 0.30 × 0.20 mm
Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.908, Tmax = 0.959

  • 32428 measured reflections

  • 6449 independent reflections

  • 5355 reflections with I > 2σ(I)

  • Rint = 0.024
Refinement

  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.109

  • S = 1.05

  • 6449 reflections

  • 181 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.44 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H2⋯O1i 0.83 (1) 2.38 (1) 3.0717 (8) 140 (1)
Symmetry code: (i) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004960/fl2185sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004960/fl2185Isup2.hkl

checkCIF report


Comment top

We are interested in the coordination chemistry of thiophene containing ligands as precursors to interesting metallopolymers. The title compound (I, Fig. 1) features a pyridine-2-carbonohydrazide moiety grafted onto the 3 position of the thiophene ring and offers a number of possible coordination modes to metal ions, which we are currently exploring.

Bond lengths and angles are in the normal range reported for other molecules containing the pyridine-2-carbonohydrazide moiety (Xie et al., 2006; Zhang et al., 2006). Bond parameters within the thiophene and pyridine rings are also within normal ranges. The C5 - N1 bond is 1.284 (8) Å, typical for a double bond and features the expected trans configuration. The C6 - N2 bond of 1.356 (8) Å is in the range between the expected values for purely single or double bonds as a result of the π-conjugation. The molecule is nearly planar; the angle between the thiophene and pyridine ring is 8.63° (4). The structure is stabilized by an intermolecular hydrogen-bond (H2···O1 = 2.38 (1) Å) between the amide hydrogen and carbonyl oxygen atoms. Other weak intermolecular interactions are suggested by close contacts between H4···N1 (2.591 (14) Å) and H5···O1 (2.609 (12) Å), Fig. 2. The structure is further stabilized by π-π interactions between adjacent thiophene rings (ring centroids are 3.6720(0.0818 Å apart).

Related literature top

The preparation and coordination chemistry of a similar compound containing a 2-substituted thiophene was reported previously by El-Motaleb, Ramadan & Issa (2005); however, no structural details were provided. For related literature and structures of other molecules containing the pyridine-2-carbonohydrazide moiety, see: Klingele & Brooker (2004); Xie et al. (2006); Zhang et al. (2006).

Experimental top

Pyridine-2-carbonohydrazide (Klingele & Brooker, 2004) (2.28 g, 16.6 mmol)was dissolved in 50 ml of absolute ethanol and cooled in an ice-water bath. A solution of 3-formylthiophene (2.91 g, 17.0 mmol) in 25 ml of absolute ethanol was added slowly dropwise to the cold hydrazide solution. Following the addition the ice-water bath was removed and the reaction was let stir at room temperature for 4 hr. While warming to room temperature, the appearance of a white microcrystalline precipitate was observed. The reaction flask was cooled in ice and the product was isolated by vacuum filtration, washed with cold ethanol and dried (yield 2.5 g, 65%). The compound was recrystallized by slow evaporation of a methanol solution to give large transparent blocks. MS (EI) = m/z 231 (M+, 20%), 79 (py+, 100%). FT—IR (KBr pellet) = 3295 (w, νN-H), 3072 (w), 1677 (s, νC=O), 1607 (m), 1533 (s), 1344 (m), 799 (m), 741 (m), 603 cm-1 (m). 1H NMR (CDCl3) = δ 10.91 (s, 1H, N—H), 8.60 (d, 1H, Ar—H), 8.42 (s, 1H, H—C=N), 8.33 (d, 1H, Ar—H), 7.92 (dd, 1H, Ar—H), 7.70 (d, 1H, Ar—H), 7.66 (d, 1H, Ar—H), 7.5 (dd, 1H, Ar—H), 7.38 (dd, 1H, Ar—H).

Refinement top

All non-hydrogen atoms were refined using anisotropic thermal parameters and hydrogen atoms were determined using the difference map and refined using isotropic thermal parameters.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of the title compound viewed along the c axis. The intermolecular hydrogen bond (N2—H2···O1) and other close contacts (H4···N1 and H5···O1) are indicated as dotted lines.
N'-(3-Thienylmethylene)pyridine-2-carbohydrazide top
Crystal data top
C11H9N3OSF(000) = 480
Mr = 231.27Dx = 1.464 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9922 reflections
a = 11.6817 (3) Åθ = 2.9–39.5°
b = 9.1454 (3) ŵ = 0.29 mm−1
c = 10.0890 (3) ÅT = 173 K
β = 103.230 (1)°Block, colourless
V = 1049.24 (5) Å30.40 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6449 independent reflections
Radiation source: fine-focus sealed tube5355 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ϕ and ω scansθmax = 40.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −21→20
Tmin = 0.908, Tmax = 0.959k = −16→16
32428 measured reflectionsl = −18→14
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0599P)2 + 0.1403P]
where P = (Fo2 + 2Fc2)/3
6449 reflections(Δ/σ)max = 0.001
181 parametersΔρmax = 0.48 e Å−3
0 restraintsΔρmin = −0.44 e Å−3
Crystal data top
C11H9N3OSV = 1049.24 (5) Å3
Mr = 231.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.6817 (3) ŵ = 0.29 mm−1
b = 9.1454 (3) ÅT = 173 K
c = 10.0890 (3) Å0.40 × 0.30 × 0.20 mm
β = 103.230 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		6449 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		5355 reflections with I > 2σ(I)
Tmin = 0.908, Tmax = 0.959Rint = 0.024
32428 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.48 e Å−3
6449 reflectionsΔρmin = −0.44 e Å−3
181 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
S10.463771 (16)0.23464 (2)0.454041 (19)0.02568 (5)
O10.85993 (5)0.78873 (6)0.23484 (5)0.02601 (10)
C10.58685 (6)0.33166 (8)0.52713 (7)0.02334 (11)
H10.6218 (12)0.3226 (15)0.6255 (14)0.038 (3)*
N10.76136 (5)0.59050 (6)0.38381 (5)0.01975 (9)
N20.86362 (5)0.66685 (7)0.43407 (6)0.02150 (10)
H20.8983 (11)0.6677 (15)0.5159 (14)0.041 (3)*
C20.62431 (5)0.41837 (7)0.43437 (6)0.01909 (9)
C30.54986 (6)0.40473 (8)0.30101 (6)0.02346 (11)
H30.5598 (11)0.4576 (15)0.2219 (14)0.038 (3)*
N31.06794 (5)0.77731 (7)0.55311 (6)0.02522 (11)
C40.45955 (6)0.30881 (8)0.29705 (7)0.02585 (12)
H40.4001 (12)0.2786 (15)0.2207 (14)0.039 (3)*
C50.72865 (5)0.50925 (7)0.47217 (6)0.02064 (10)
H50.7741 (11)0.5050 (14)0.5620 (12)0.032 (3)*
C60.90780 (5)0.75931 (7)0.35325 (6)0.01910 (10)
C71.02436 (5)0.82307 (7)0.42481 (6)0.01914 (10)
C81.08096 (6)0.92324 (8)0.35862 (7)0.02498 (12)
H81.0462 (10)0.9482 (14)0.2685 (12)0.030 (3)*
C91.18816 (7)0.98075 (9)0.42927 (9)0.02855 (13)
H91.2275 (12)1.0512 (16)0.3916 (13)0.040 (3)*
C101.23335 (6)0.93561 (9)0.56184 (9)0.02901 (13)
H101.3068 (12)0.9703 (17)0.6115 (13)0.042 (4)*
C111.17048 (6)0.83398 (10)0.61907 (8)0.02998 (14)
H111.2008 (13)0.7924 (18)0.7155 (16)0.050 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.02498 (8)0.02603 (8)0.02706 (9)−0.00757 (5)0.00809 (6)−0.00236 (5)
O10.0262 (2)0.0318 (2)0.01804 (19)−0.00370 (18)0.00077 (16)0.00251 (17)
C10.0225 (2)0.0263 (3)0.0206 (2)−0.0040 (2)0.00363 (19)0.0013 (2)
N10.01699 (19)0.0214 (2)0.0198 (2)−0.00233 (16)0.00210 (15)−0.00098 (16)
N20.0187 (2)0.0259 (2)0.0182 (2)−0.00545 (17)0.00069 (16)0.00143 (17)
C20.0182 (2)0.0192 (2)0.0193 (2)−0.00147 (17)0.00317 (17)−0.00077 (17)
C30.0258 (3)0.0244 (3)0.0189 (2)−0.0053 (2)0.00249 (19)−0.00152 (19)
N30.0194 (2)0.0311 (3)0.0230 (2)−0.00334 (19)0.00019 (17)0.0037 (2)
C40.0265 (3)0.0271 (3)0.0223 (3)−0.0072 (2)0.0022 (2)−0.0045 (2)
C50.0191 (2)0.0224 (2)0.0193 (2)−0.00278 (18)0.00200 (17)−0.00012 (18)
C60.0181 (2)0.0202 (2)0.0184 (2)−0.00070 (17)0.00300 (17)−0.00088 (17)
C70.0173 (2)0.0199 (2)0.0199 (2)−0.00059 (17)0.00357 (17)−0.00080 (17)
C80.0246 (3)0.0252 (3)0.0248 (3)−0.0050 (2)0.0050 (2)0.0016 (2)
C90.0240 (3)0.0273 (3)0.0346 (3)−0.0067 (2)0.0072 (2)0.0005 (2)
C100.0191 (2)0.0302 (3)0.0355 (3)−0.0043 (2)0.0017 (2)−0.0033 (3)
C110.0210 (3)0.0380 (4)0.0271 (3)−0.0042 (2)−0.0023 (2)0.0025 (3)
Geometric parameters (Å, º) top
S1—C11.7067 (7)N3—C111.3347 (9)
S1—C41.7133 (8)N3—C71.3446 (9)
O1—C61.2274 (8)C4—H40.953 (14)
C1—C21.3724 (9)C5—H50.941 (12)
C1—H10.987 (13)C6—C71.5052 (8)
N1—C51.2841 (8)C7—C81.3873 (9)
N1—N21.3764 (7)C8—C91.3944 (10)
N2—C61.3559 (8)C8—H80.935 (12)
N2—H20.832 (14)C9—C101.3838 (12)
C2—C31.4306 (9)C9—H90.922 (14)
C2—C51.4523 (8)C10—C111.3895 (11)
C3—C41.3655 (10)C10—H100.944 (14)
C3—H30.963 (14)C11—H111.029 (15)
H4···N1i2.591 (14)H5···O1ii2.609 (12)
C1—S1—C492.11 (3)C2—C5—H5119.0 (8)
C2—C1—S1111.98 (5)O1—C6—N2124.80 (6)
C2—C1—H1127.7 (8)O1—C6—C7122.86 (6)
S1—C1—H1120.3 (8)N2—C6—C7112.34 (5)
C5—N1—N2114.13 (5)N3—C7—C8123.49 (6)
C6—N2—N1120.83 (5)N3—C7—C6116.28 (5)
C6—N2—H2115.1 (9)C8—C7—C6120.23 (6)
N1—N2—H2123.7 (9)C7—C8—C9118.31 (7)
C1—C2—C3111.77 (6)C7—C8—H8118.7 (7)
C1—C2—C5122.07 (6)C9—C8—H8123.0 (7)
C3—C2—C5126.15 (6)C10—C9—C8118.74 (7)
C4—C3—C2112.51 (6)C10—C9—H9119.4 (8)
C4—C3—H3122.5 (8)C8—C9—H9121.8 (8)
C2—C3—H3124.9 (8)C9—C10—C11118.70 (7)
C11—N3—C7117.26 (6)C9—C10—H10120.8 (8)
C3—C4—S1111.64 (5)C11—C10—H10120.5 (8)
C3—C4—H4128.8 (8)N3—C11—C10123.50 (7)
S1—C4—H4119.6 (8)N3—C11—H11113.8 (9)
N1—C5—C2120.94 (6)C10—C11—H11122.7 (8)
N1—C5—H5120.0 (8)
C4—S1—C1—C2−0.15 (6)C11—N3—C7—C80.86 (11)
C5—N1—N2—C6−178.74 (6)C11—N3—C7—C6−179.13 (7)
S1—C1—C2—C30.21 (8)O1—C6—C7—N3−177.94 (7)
S1—C1—C2—C5−178.92 (5)N2—C6—C7—N31.78 (8)
C1—C2—C3—C4−0.17 (9)O1—C6—C7—C82.06 (10)
C5—C2—C3—C4178.92 (7)N2—C6—C7—C8−178.21 (6)
C2—C3—C4—S10.05 (8)N3—C7—C8—C9−0.69 (11)
C1—S1—C4—C30.05 (6)C6—C7—C8—C9179.30 (6)
N2—N1—C5—C2−178.20 (6)C7—C8—C9—C100.02 (11)
C1—C2—C5—N1−179.36 (6)C8—C9—C10—C110.42 (12)
C3—C2—C5—N11.64 (11)C7—N3—C11—C10−0.38 (13)
N1—N2—C6—O13.95 (11)C9—C10—C11—N3−0.25 (13)
N1—N2—C6—C7−175.76 (5)
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1ii0.83 (1)2.38 (1)3.0717 (8)140 (1)
Symmetry code: (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC11H9N3OS
Mr231.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)11.6817 (3), 9.1454 (3), 10.0890 (3)
β (°) 103.230 (1)
V (Å3)1049.24 (5)
Z4
Radiation typeMo Kα
µ (mm−1)0.29
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.908, 0.959
No. of measured, independent and
observed [I > 2σ(I)] reflections		32428, 6449, 5355
Rint0.024
(sin θ/λ)max (Å−1)0.914
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.109, 1.05
No. of reflections6449
No. of parameters181
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.48, −0.44

Computer programs: APEX2 (Bruker, 2006), SHELXTL (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.83 (1)2.38 (1)3.0717 (8)140 (1)
Symmetry code: (i) x, −y+3/2, z+1/2.
 

Acknowledgements

The authors thank the Natural Sciences and Engineering Research Council for financial support. Martin Lemaire thanks Brock University and Research Corporation for a Cottrell College grant (No. CC6686) in support of this research. The X-ray crystallographic analyses were performed at the McMaster Analytical X-ray (MAX) Diffraction Facility.

References

First citationBruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationEl-Motaleb, A., Ramadan, M. & Issa, R. M. (2005). Transition Met. Chem. 30, 471–480.  Web of Science CrossRef CAS Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationKlingele, M. H. & Brooker, S. (2004). Eur. J. Org. Chem. pp. 3422–3434.  Web of Science CSD CrossRef Google Scholar
 First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationXie, Y.-Q., Sheng, L.-Q., Zhu, W. & Shao, S.-C. (2006). Acta Cryst. E62, o26–o27.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationZhang, J., Ma, C.-A., Song, Q.-B. & Tiekink, E. R. T. (2006). Acta Cryst. E62, o2644–o2645.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 4| April 2008| Page o719
doi:10.1107/S1600536808004960
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