organic compounds
N-{(Z)-3-Oxo-3-[(E)-(pyridin-2-ylmethyl)diazenyl]-1-(thiophen-2-yl)prop-1-en-2-yl}benzamide
aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, bDepartment of Chemistry, Mangalore University, Mangalagangothri 574 199, Mangalore, India, and cDepartment of Studies in Chemistry–Industrial Chemistry, Mangalore University, Mangalagangothri 574 199, India
*Correspondence e-mail: rkant.ju@gmail.com
In the title compound, C20H16N4O2S, the thiophene ring subtends dihedral angles of 58.6 (3) and 9.8 (3)° with the benzamide and pyridine rings, respectively, whereas these two rings are inclined to one another by 59.3 (3)°. There is an intramolecular C—H⋯π interaction present involving the pyridine and benzamide rings. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains along the [010] direction. The chains are linked by C—H⋯S hydrogen bonds and C—H⋯π interactions, forming sheets parallel to the ab plane.
Keywords: crystal structure; diazo; benzamide; hydrogen bonding; C—H⋯π interactions.
CCDC reference: 1498199
Structure description
etc (Wang et al., 2000). The title compound is initially a hydrazone formed by the reaction of the precursor hydrazide 1 with pyridine 2-aldehyde (see Scheme). However, it rearranges to a diazo derivative by a 1,3 proton shift. Herein, we report on the of compound 2, containing a diazo (–N=N–) linkage.
have a (–N=N–) linkage, and are highly coloured compounds. They are used as dyes and pigments for colouring fibers, optical storage devices, photo-electronic applications, printing systems, textile dyesIn the title compound, Fig. 1, the thiophene ring forms a dihedral angle 9.8 (3)° with the pyridine ring. The benzamide ring is inclined to the thiophene and pyridine rings by 58.6 (3) and 59.3 (3)°, respectively. The molecule has an E conformation about the N1=N2 bond, and a Z conformation about the C5=C6 bond. There is an intramolecular C—H⋯π interaction present involving the pyridine and benzamide rings (Fig. 1 and Table 1).
In the crystal, molecules are linked by N—H⋯O hydrogen bonds forming chains along the b-axis direction (Fig. 2 and Table 1). The chains are linked by C—H⋯S hydrogen bonds and C—H⋯π interactions, forming sheets parallel to the ab plane (Fig. 2 and Table 1).
Synthesis and crystallization
A mixture of [3-hydrazinyl-3-oxo-1-(thiophen-2-yl)prop-1-en-2-yl]benzamide 1 (2.87 g, 0.01 mol), and pyridine-2-carbaldehyde (1.07 g, 0.01 mol) in 20 ml ethanol were stirred for 3–4 h. The solid obtained was filtered, washed with cold water, dried and recrystallized from ethanol. Single crystals of 2 were grown from a methanol–1,4-dioxane (1:1) mixture by slow evaporation (m.p. 507–508 K).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1498199
10.1107/S2414314616012761/su4067sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616012761/su4067Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616012761/su4067Isup3.cml
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C20H16N4O2S | F(000) = 392 |
Mr = 376.43 | Dx = 1.378 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 985 reflections |
a = 9.3289 (10) Å | θ = 4.4–26.3° |
b = 9.9031 (10) Å | µ = 0.20 mm−1 |
c = 9.8984 (12) Å | T = 293 K |
β = 97.221 (11)° | Rectangular, brown |
V = 907.21 (17) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 2 |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 2547 independent reflections |
Radiation source: fine-focus sealed tube | 1807 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 16.1049 pixels mm-1 | θmax = 26.0°, θmin = 3.5° |
ω scans | h = −9→11 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | k = −6→12 |
Tmin = 0.749, Tmax = 1.000 | l = −11→12 |
3602 measured reflections |
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) = 0.137 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0485P)2] where P = (Fo2 + 2Fc2)/3 |
2547 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.30 e Å−3 |
1 restraint | Δρmin = −0.27 e Å−3 |
Experimental. CrysAlis Pro (Oxford Diffraction, 2010) |
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 > 2sigma(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 | 0.53359 (14) | 0.16714 (15) | 1.01498 (14) | 0.0554 (4) | |
N1 | 1.0902 (4) | 0.3655 (4) | 1.0744 (4) | 0.0444 (10) | |
N4 | 0.8437 (4) | 0.2341 (4) | 1.1093 (4) | 0.0397 (9) | |
H4 | 0.8568 | 0.1485 | 1.1021 | 0.048* | |
O2 | 0.7951 (5) | 0.4099 (3) | 1.2397 (4) | 0.0637 (11) | |
O1 | 0.9821 (4) | 0.4880 (4) | 0.8927 (4) | 0.0664 (11) | |
N2 | 1.2188 (5) | 0.4370 (4) | 1.0774 (4) | 0.0493 (11) | |
N3 | 1.2102 (4) | 0.2226 (4) | 1.2834 (4) | 0.0473 (11) | |
C9 | 1.3313 (5) | 0.2957 (5) | 1.2705 (5) | 0.0446 (12) | |
C8 | 1.3214 (5) | 0.4001 (5) | 1.1653 (5) | 0.0484 (13) | |
H8A | 1.3509 | 0.4822 | 1.2145 | 0.058* | |
H8B | 1.3993 | 0.3788 | 1.1125 | 0.058* | |
C4 | 0.5869 (5) | 0.2766 (5) | 0.8944 (5) | 0.0470 (12) | |
C15 | 0.8350 (5) | 0.1983 (5) | 1.3518 (5) | 0.0401 (11) | |
C14 | 0.8217 (5) | 0.2889 (5) | 1.2308 (5) | 0.0425 (12) | |
C7 | 0.9768 (5) | 0.3999 (5) | 0.9807 (5) | 0.0421 (12) | |
C16 | 0.8130 (5) | 0.0601 (5) | 1.3426 (5) | 0.0464 (12) | |
H16 | 0.7867 | 0.0198 | 1.2583 | 0.056* | |
C5 | 0.7281 (6) | 0.3345 (5) | 0.8987 (5) | 0.0499 (13) | |
H5 | 0.7413 | 0.3901 | 0.8256 | 0.060* | |
C6 | 0.8447 (5) | 0.3205 (5) | 0.9930 (5) | 0.0408 (11) | |
C20 | 0.8724 (5) | 0.2558 (6) | 1.4772 (5) | 0.0500 (13) | |
H20 | 0.8837 | 0.3489 | 1.4842 | 0.060* | |
C11 | 1.3428 (6) | 0.1005 (6) | 1.4664 (6) | 0.0637 (16) | |
H11 | 1.3449 | 0.0342 | 1.5332 | 0.076* | |
C13 | 1.4587 (6) | 0.2743 (6) | 1.3537 (6) | 0.0564 (14) | |
H13 | 1.5398 | 0.3260 | 1.3436 | 0.068* | |
C17 | 0.8305 (6) | −0.0174 (6) | 1.4596 (6) | 0.0602 (15) | |
H17 | 0.8129 | −0.1098 | 1.4541 | 0.072* | |
C1 | 0.3663 (6) | 0.1528 (6) | 0.9289 (6) | 0.0634 (16) | |
H1 | 0.2947 | 0.0985 | 0.9578 | 0.076* | |
C3 | 0.4727 (6) | 0.3004 (6) | 0.7921 (6) | 0.0612 (15) | |
H3 | 0.4781 | 0.3572 | 0.7180 | 0.073* | |
C10 | 1.2185 (6) | 0.1270 (5) | 1.3791 (6) | 0.0559 (15) | |
H10 | 1.1365 | 0.0757 | 1.3875 | 0.067* | |
C19 | 0.8932 (5) | 0.1783 (7) | 1.5915 (5) | 0.0640 (16) | |
H19 | 0.9211 | 0.2184 | 1.6757 | 0.077* | |
C18 | 0.8731 (6) | 0.0402 (6) | 1.5827 (6) | 0.0633 (16) | |
H18 | 0.8887 | −0.0130 | 1.6605 | 0.076* | |
C12 | 1.4648 (6) | 0.1767 (8) | 1.4506 (6) | 0.0671 (16) | |
H12 | 1.5508 | 0.1608 | 1.5067 | 0.081* | |
C2 | 0.3467 (6) | 0.2271 (7) | 0.8149 (7) | 0.0764 (19) | |
H2 | 0.2602 | 0.2304 | 0.7570 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0574 (8) | 0.0551 (8) | 0.0545 (8) | −0.0009 (7) | 0.0105 (7) | 0.0024 (7) |
N1 | 0.040 (2) | 0.045 (2) | 0.048 (3) | −0.004 (2) | 0.0056 (19) | 0.003 (2) |
N4 | 0.049 (2) | 0.035 (2) | 0.036 (2) | 0.0003 (18) | 0.0091 (19) | 0.0022 (18) |
O2 | 0.102 (3) | 0.0386 (19) | 0.051 (2) | 0.020 (2) | 0.012 (2) | 0.0004 (19) |
O1 | 0.063 (2) | 0.068 (3) | 0.066 (3) | −0.020 (2) | 0.002 (2) | 0.028 (2) |
N2 | 0.048 (3) | 0.046 (3) | 0.055 (3) | −0.005 (2) | 0.012 (2) | 0.008 (2) |
N3 | 0.045 (2) | 0.046 (2) | 0.050 (3) | 0.003 (2) | 0.004 (2) | 0.006 (2) |
C9 | 0.043 (3) | 0.049 (3) | 0.043 (3) | −0.003 (2) | 0.012 (2) | 0.000 (3) |
C8 | 0.044 (3) | 0.053 (3) | 0.050 (3) | 0.002 (2) | 0.014 (3) | 0.005 (3) |
C4 | 0.051 (3) | 0.050 (3) | 0.040 (3) | −0.004 (3) | 0.003 (2) | −0.001 (2) |
C15 | 0.037 (2) | 0.046 (3) | 0.040 (3) | 0.003 (2) | 0.011 (2) | 0.009 (2) |
C14 | 0.044 (3) | 0.039 (3) | 0.044 (3) | −0.001 (2) | 0.002 (2) | 0.004 (2) |
C7 | 0.043 (3) | 0.042 (3) | 0.042 (3) | −0.007 (2) | 0.008 (2) | 0.007 (2) |
C16 | 0.047 (3) | 0.044 (3) | 0.048 (3) | 0.001 (2) | 0.007 (2) | 0.006 (3) |
C5 | 0.060 (3) | 0.050 (3) | 0.039 (3) | 0.000 (3) | 0.006 (3) | −0.002 (3) |
C6 | 0.050 (3) | 0.041 (3) | 0.032 (2) | 0.002 (2) | 0.007 (2) | 0.005 (2) |
C20 | 0.052 (3) | 0.056 (3) | 0.043 (3) | 0.000 (3) | 0.006 (2) | 0.002 (3) |
C11 | 0.060 (4) | 0.068 (4) | 0.061 (4) | 0.008 (3) | 0.002 (3) | 0.016 (3) |
C13 | 0.043 (3) | 0.073 (4) | 0.052 (3) | 0.004 (3) | 0.000 (3) | 0.000 (3) |
C17 | 0.057 (3) | 0.062 (4) | 0.062 (4) | −0.005 (3) | 0.011 (3) | 0.026 (3) |
C1 | 0.058 (3) | 0.060 (4) | 0.072 (4) | −0.009 (3) | 0.007 (3) | −0.005 (4) |
C3 | 0.055 (3) | 0.066 (4) | 0.059 (4) | −0.005 (3) | −0.006 (3) | 0.006 (3) |
C10 | 0.057 (3) | 0.048 (3) | 0.064 (4) | −0.001 (3) | 0.011 (3) | 0.010 (3) |
C19 | 0.063 (3) | 0.094 (5) | 0.036 (3) | −0.005 (4) | 0.008 (3) | −0.006 (3) |
C18 | 0.063 (4) | 0.069 (4) | 0.059 (4) | 0.001 (3) | 0.011 (3) | 0.031 (3) |
C12 | 0.047 (3) | 0.086 (4) | 0.066 (4) | 0.014 (4) | −0.006 (3) | 0.001 (4) |
C2 | 0.059 (4) | 0.090 (5) | 0.074 (4) | −0.007 (4) | −0.015 (3) | −0.001 (4) |
S1—C1 | 1.687 (5) | C16—H16 | 0.9300 |
S1—C4 | 1.731 (5) | C5—C6 | 1.349 (7) |
N1—C7 | 1.359 (7) | C5—H5 | 0.9300 |
N1—N2 | 1.389 (5) | C20—C19 | 1.361 (7) |
N4—C14 | 1.359 (6) | C20—H20 | 0.9300 |
N4—C6 | 1.436 (6) | C11—C10 | 1.382 (7) |
N4—H4 | 0.8600 | C11—C12 | 1.390 (8) |
O2—C14 | 1.229 (5) | C11—H11 | 0.9300 |
O1—C7 | 1.238 (6) | C13—C12 | 1.358 (8) |
N2—C8 | 1.264 (6) | C13—H13 | 0.9300 |
N3—C10 | 1.335 (6) | C17—C18 | 1.358 (8) |
N3—C9 | 1.362 (6) | C17—H17 | 0.9300 |
C9—C13 | 1.374 (6) | C1—C2 | 1.341 (8) |
C9—C8 | 1.462 (6) | C1—H1 | 0.9300 |
C8—H8A | 0.9700 | C3—C2 | 1.423 (8) |
C8—H8B | 0.9700 | C3—H3 | 0.9300 |
C4—C3 | 1.395 (7) | C10—H10 | 0.9300 |
C4—C5 | 1.432 (7) | C19—C18 | 1.382 (9) |
C15—C20 | 1.370 (6) | C19—H19 | 0.9300 |
C15—C16 | 1.385 (7) | C18—H18 | 0.9300 |
C15—C14 | 1.490 (6) | C12—H12 | 0.9300 |
C7—C6 | 1.479 (7) | C2—H2 | 0.9300 |
C16—C17 | 1.382 (7) | ||
C1—S1—C4 | 91.9 (3) | C5—C6—C7 | 119.8 (5) |
C7—N1—N2 | 118.9 (4) | N4—C6—C7 | 118.2 (4) |
C14—N4—C6 | 119.2 (4) | C19—C20—C15 | 120.8 (5) |
C14—N4—H4 | 120.4 | C19—C20—H20 | 119.6 |
C6—N4—H4 | 120.4 | C15—C20—H20 | 119.6 |
C8—N2—N1 | 116.4 (4) | C10—C11—C12 | 117.4 (5) |
C10—N3—C9 | 118.0 (4) | C10—C11—H11 | 121.3 |
N3—C9—C13 | 121.8 (5) | C12—C11—H11 | 121.3 |
N3—C9—C8 | 117.6 (4) | C12—C13—C9 | 119.3 (5) |
C13—C9—C8 | 120.6 (5) | C12—C13—H13 | 120.4 |
N2—C8—C9 | 132.0 (5) | C9—C13—H13 | 120.4 |
N2—C8—H8A | 104.2 | C18—C17—C16 | 120.6 (5) |
C9—C8—H8A | 104.2 | C18—C17—H17 | 119.7 |
N2—C8—H8B | 104.2 | C16—C17—H17 | 119.7 |
C9—C8—H8B | 104.2 | C2—C1—S1 | 113.5 (5) |
H8A—C8—H8B | 105.5 | C2—C1—H1 | 123.3 |
C3—C4—C5 | 124.7 (5) | S1—C1—H1 | 123.3 |
C3—C4—S1 | 110.3 (4) | C4—C3—C2 | 111.7 (6) |
C5—C4—S1 | 125.0 (4) | C4—C3—H3 | 124.2 |
C20—C15—C16 | 119.3 (5) | C2—C3—H3 | 124.2 |
C20—C15—C14 | 117.6 (4) | N3—C10—C11 | 123.2 (5) |
C16—C15—C14 | 123.1 (4) | N3—C10—H10 | 118.4 |
O2—C14—N4 | 120.5 (4) | C11—C10—H10 | 118.4 |
O2—C14—C15 | 121.8 (5) | C20—C19—C18 | 120.1 (5) |
N4—C14—C15 | 117.7 (4) | C20—C19—H19 | 120.0 |
O1—C7—N1 | 124.0 (4) | C18—C19—H19 | 120.0 |
O1—C7—C6 | 122.6 (5) | C17—C18—C19 | 119.6 (5) |
N1—C7—C6 | 113.3 (4) | C17—C18—H18 | 120.2 |
C17—C16—C15 | 119.5 (5) | C19—C18—H18 | 120.2 |
C17—C16—H16 | 120.2 | C13—C12—C11 | 120.2 (5) |
C15—C16—H16 | 120.2 | C13—C12—H12 | 119.9 |
C6—C5—C4 | 129.7 (5) | C11—C12—H12 | 119.9 |
C6—C5—H5 | 115.2 | C1—C2—C3 | 112.7 (5) |
C4—C5—H5 | 115.2 | C1—C2—H2 | 123.7 |
C5—C6—N4 | 122.0 (5) | C3—C2—H2 | 123.7 |
C7—N1—N2—C8 | −179.2 (5) | C14—N4—C6—C7 | 78.7 (5) |
C10—N3—C9—C13 | −0.8 (7) | O1—C7—C6—C5 | 6.0 (8) |
C10—N3—C9—C8 | 179.9 (4) | N1—C7—C6—C5 | −173.6 (4) |
N1—N2—C8—C9 | −1.9 (8) | O1—C7—C6—N4 | −171.7 (5) |
N3—C9—C8—N2 | −1.5 (8) | N1—C7—C6—N4 | 8.7 (6) |
C13—C9—C8—N2 | 179.2 (5) | C16—C15—C20—C19 | 2.4 (8) |
C1—S1—C4—C3 | 0.9 (4) | C14—C15—C20—C19 | −176.8 (5) |
C1—S1—C4—C5 | −179.0 (5) | N3—C9—C13—C12 | 0.6 (8) |
C6—N4—C14—O2 | 4.0 (7) | C8—C9—C13—C12 | 179.9 (5) |
C6—N4—C14—C15 | −174.4 (4) | C15—C16—C17—C18 | −2.0 (8) |
C20—C15—C14—O2 | −24.7 (7) | C4—S1—C1—C2 | −0.8 (5) |
C16—C15—C14—O2 | 156.1 (5) | C5—C4—C3—C2 | 179.1 (5) |
C20—C15—C14—N4 | 153.6 (4) | S1—C4—C3—C2 | −0.8 (6) |
C16—C15—C14—N4 | −25.6 (7) | C9—N3—C10—C11 | 1.0 (7) |
N2—N1—C7—O1 | 3.3 (8) | C12—C11—C10—N3 | −1.1 (9) |
N2—N1—C7—C6 | −177.1 (4) | C15—C20—C19—C18 | −1.7 (9) |
C20—C15—C16—C17 | −0.6 (7) | C16—C17—C18—C19 | 2.7 (9) |
C14—C15—C16—C17 | 178.6 (5) | C20—C19—C18—C17 | −0.9 (9) |
C3—C4—C5—C6 | 178.8 (5) | C9—C13—C12—C11 | −0.7 (9) |
S1—C4—C5—C6 | −1.3 (8) | C10—C11—C12—C13 | 0.9 (9) |
C4—C5—C6—N4 | 2.4 (8) | S1—C1—C2—C3 | 0.5 (7) |
C4—C5—C6—C7 | −175.1 (5) | C4—C3—C2—C1 | 0.2 (8) |
C14—N4—C6—C5 | −98.9 (5) |
Cg2 and Cg3 are the centroids of rings N3/C9–C13 and C15–C20, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O1i | 0.86 | 2.18 | 2.931 (6) | 145 |
C8—H8B···S1ii | 0.97 | 2.68 | 3.492 (5) | 141 |
C10—H10···Cg3 | 0.93 | 2.89 | 3.627 (6) | 137 |
C12—H12···Cg2ii | 0.93 | 2.92 | 3.648 (6) | 136 |
Symmetry codes: (i) −x+2, y−1/2, −z+2; (ii) x+1, y, z. |
Acknowledgements
RK acknowledges the Indian Council of Medical Research, New Delhi, for financial support [research project No. BIC/12 (14)/2012] and the Department of Science and Technology Research (project No. EMR/2014/000467). KNS gratefully acknowledges the Department of Chemistry, Shri Madhwa Vadiraja Institute of Technology, Bantakal (VTU Belgam), for providing research facilities.
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