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organic compounds
(E,E)-N′-{4-[(2-Benzoylhydrazin-1-ylidene)methyl]benzylidene}benzohydrazide
aApplied Biotechnology Research Center, Baqiyatallah University of Medical Sciences, Tehran, Iran, bDepartment of Chemistry, University of Zanjan, 45195-313 Zanjan, Iran, cYoung Researchers Club, Tabriz Branch, Islamic Azad University, Tabriz, Iran, and dDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, 55019 Kurupelit, Samsun, Turkey
*Correspondence e-mail: bikas_r@yahoo.com
In the title compound, C22H18N4O2, the molecules lie across an inversion centre. The dihedral angle between the mean planes of the central and terminal benzene rings is 66.03 (2)°. The molecule displays trans and anti conformations about the C=N and N—N bonds, respectively. In the crystal, N—H⋯O hydrogen bonds, with the O atoms of C=O groups acting as acceptors, link the molecules into a chain along [101].
Related literature
For historical background to aroylhydrazones, see: Savanini et al. (2002). For related structures, see: Bikas et al. (2012
, 2010a
,b
); Hosseini Monfared et al. (2010a
). For catalytic applications of aroylhydrazones, see: Hosseini Monfared et al. (2010b
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002
); 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, 1997
); software used to prepare material for publication: WinGX (Farrugia, 1999
) and PLATON (Spek, 2009
).
Supporting information
10.1107/S1600536812014687/qm2059sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812014687/qm2059Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812014687/qm2059Isup3.cml
For preparing the title compound a methanol (10 ml) solution of benzhydrazide (3 mmol) was added drop-wise to a methanol solution (10 ml) of terephthalaldehyde (1.5 mmol), and the mixture was refluxed for 4 h. The solution was then evaporated on a steam bath to 5 cm3 and cooled to room temperature. The white precipitates of the title compound were separated and filtered off, washed with 3 ml of cooled methanol and then dried in air. Colorless crystals were obtained from its methanol solution by thermal gradient method. Yield: 93%. IR (cm-1): 3253 (s, broad, N—H), 1654 (vs, C=O), 1607 (s, C=N), 1546 (vs), 1507 (m), 1361 (s), 1284 (vs), 1146 (s), 1069 (s), 969 (m), 915 (m), 846 (m), 723 (s), 692 (s), 661 (s), 569 (w), 538 (w), 423 (w).
Data collection: X-AREA (Stoe & Cie, 2002); cell
X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).C22H18N4O2 | F(000) = 776 |
Mr = 370.40 | Dx = 1.341 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 8004 reflections |
a = 30.569 (3) Å | θ = 1.4–27.5° |
b = 5.1845 (3) Å | µ = 0.09 mm−1 |
c = 12.5191 (11) Å | T = 293 K |
β = 112.408 (7)° | Prism, colorless |
V = 1834.3 (3) Å3 | 0.42 × 0.22 × 0.08 mm |
Z = 4 |
Stoe IPDS 2 diffractometer | 1905 independent reflections |
Radiation source: fine-focus sealed tube | 965 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.105 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.5°, θmin = 1.4° |
rotation method scans | h = −38→38 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −6→6 |
Tmin = 0.976, Tmax = 0.992 | l = −15→15 |
13265 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | All H-atom parameters refined |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0207P)2] where P = (Fo2 + 2Fc2)/3 |
1905 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.11 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C22H18N4O2 | V = 1834.3 (3) Å3 |
Mr = 370.40 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.569 (3) Å | µ = 0.09 mm−1 |
b = 5.1845 (3) Å | T = 293 K |
c = 12.5191 (11) Å | 0.42 × 0.22 × 0.08 mm |
β = 112.408 (7)° |
Stoe IPDS 2 diffractometer | 1905 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 965 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.992 | Rint = 0.105 |
13265 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.078 | All H-atom parameters refined |
S = 0.94 | Δρmax = 0.11 e Å−3 |
1905 reflections | Δρmin = −0.14 e Å−3 |
163 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.84753 (7) | 0.1985 (4) | 0.32678 (19) | 0.0454 (6) | |
C2 | 0.84744 (9) | 0.3457 (5) | 0.4191 (2) | 0.0562 (7) | |
C3 | 0.81956 (9) | 0.2794 (6) | 0.4790 (2) | 0.0658 (8) | |
C4 | 0.79059 (10) | 0.0693 (6) | 0.4454 (3) | 0.0695 (8) | |
C5 | 0.78956 (10) | −0.0782 (5) | 0.3532 (3) | 0.0711 (8) | |
C6 | 0.81817 (8) | −0.0140 (5) | 0.2948 (2) | 0.0582 (7) | |
C7 | 0.87799 (7) | 0.2804 (4) | 0.26408 (19) | 0.0475 (6) | |
C8 | 0.94196 (8) | −0.0556 (5) | 0.1321 (2) | 0.0502 (6) | |
C10 | 0.96656 (9) | 0.1846 (5) | −0.0081 (2) | 0.0558 (7) | |
C11 | 1.00525 (9) | −0.2099 (5) | 0.0707 (2) | 0.0553 (7) | |
C12 | 0.97114 (7) | −0.0250 (4) | 0.06315 (18) | 0.0458 (6) | |
N1 | 0.89465 (7) | 0.0866 (4) | 0.21865 (17) | 0.0543 (6) | |
N2 | 0.92141 (7) | 0.1407 (3) | 0.15428 (16) | 0.0516 (5) | |
O1 | 0.88701 (6) | 0.5082 (3) | 0.25515 (14) | 0.0650 (5) | |
H1 | 0.8912 (7) | −0.074 (4) | 0.2351 (18) | 0.055 (7)* | |
H2 | 0.9404 (6) | −0.232 (4) | 0.1624 (16) | 0.052 (6)* | |
H3 | 0.8174 (7) | −0.118 (4) | 0.2312 (19) | 0.058 (7)* | |
H4 | 0.9424 (8) | 0.305 (4) | −0.0167 (18) | 0.065 (7)* | |
H5 | 1.0094 (7) | −0.343 (4) | 0.1209 (18) | 0.056 (7)* | |
H6 | 0.8219 (8) | 0.387 (4) | 0.546 (2) | 0.078 (8)* | |
H7 | 0.8670 (7) | 0.499 (4) | 0.4386 (17) | 0.068 (7)* | |
H8 | 0.7688 (9) | −0.228 (5) | 0.324 (2) | 0.101 (10)* | |
H9 | 0.7717 (9) | 0.017 (5) | 0.489 (2) | 0.096 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0450 (14) | 0.0457 (13) | 0.0519 (16) | 0.0066 (11) | 0.0255 (13) | 0.0039 (12) |
C2 | 0.0568 (16) | 0.0572 (16) | 0.0627 (18) | −0.0026 (13) | 0.0319 (15) | −0.0062 (13) |
C3 | 0.0676 (17) | 0.0798 (19) | 0.0621 (19) | 0.0055 (16) | 0.0385 (17) | −0.0027 (16) |
C4 | 0.0691 (19) | 0.0738 (19) | 0.084 (2) | 0.0066 (15) | 0.0495 (18) | 0.0112 (17) |
C5 | 0.0715 (19) | 0.0601 (17) | 0.099 (2) | −0.0068 (15) | 0.0518 (19) | −0.0044 (17) |
C6 | 0.0618 (15) | 0.0521 (14) | 0.0735 (19) | −0.0023 (13) | 0.0401 (15) | −0.0111 (15) |
C7 | 0.0477 (13) | 0.0479 (14) | 0.0513 (16) | 0.0053 (12) | 0.0239 (12) | 0.0012 (12) |
C8 | 0.0532 (15) | 0.0486 (16) | 0.0569 (16) | 0.0007 (12) | 0.0301 (13) | −0.0008 (12) |
C10 | 0.0580 (16) | 0.0553 (15) | 0.0662 (18) | 0.0137 (13) | 0.0375 (15) | 0.0052 (13) |
C11 | 0.0655 (16) | 0.0507 (14) | 0.0605 (18) | 0.0083 (13) | 0.0362 (15) | 0.0045 (13) |
C12 | 0.0454 (14) | 0.0483 (13) | 0.0504 (15) | −0.0004 (12) | 0.0259 (12) | −0.0059 (12) |
N1 | 0.0648 (14) | 0.0476 (12) | 0.0704 (15) | 0.0036 (11) | 0.0481 (13) | 0.0054 (11) |
N2 | 0.0531 (12) | 0.0537 (12) | 0.0599 (13) | 0.0006 (9) | 0.0349 (11) | −0.0002 (10) |
O1 | 0.0857 (12) | 0.0445 (9) | 0.0850 (13) | −0.0003 (9) | 0.0552 (10) | 0.0020 (9) |
C1—C6 | 1.381 (3) | C7—N1 | 1.346 (3) |
C1—C2 | 1.386 (3) | C8—N2 | 1.281 (3) |
C1—C7 | 1.490 (3) | C8—C12 | 1.467 (3) |
C2—C3 | 1.377 (3) | C8—H2 | 1.00 (2) |
C2—H7 | 0.97 (2) | C10—C11i | 1.375 (3) |
C3—C4 | 1.365 (4) | C10—C12 | 1.379 (3) |
C3—H6 | 0.99 (2) | C10—H4 | 0.94 (2) |
C4—C5 | 1.374 (3) | C11—C10i | 1.375 (3) |
C4—H9 | 0.98 (3) | C11—C12 | 1.392 (3) |
C5—C6 | 1.378 (3) | C11—H5 | 0.91 (2) |
C5—H8 | 0.98 (3) | N1—N2 | 1.378 (2) |
C6—H3 | 0.95 (2) | N1—H1 | 0.87 (2) |
C7—O1 | 1.228 (2) | ||
C6—C1—C2 | 118.3 (2) | O1—C7—C1 | 121.95 (19) |
C6—C1—C7 | 122.8 (2) | N1—C7—C1 | 115.0 (2) |
C2—C1—C7 | 118.9 (2) | N2—C8—C12 | 120.0 (2) |
C3—C2—C1 | 121.0 (3) | N2—C8—H2 | 123.2 (11) |
C3—C2—H7 | 121.3 (13) | C12—C8—H2 | 116.7 (11) |
C1—C2—H7 | 117.7 (13) | C11i—C10—C12 | 120.8 (2) |
C4—C3—C2 | 119.6 (3) | C11i—C10—H4 | 120.5 (13) |
C4—C3—H6 | 122.6 (14) | C12—C10—H4 | 118.5 (13) |
C2—C3—H6 | 117.8 (14) | C10i—C11—C12 | 120.8 (2) |
C3—C4—C5 | 120.5 (3) | C10i—C11—H5 | 120.9 (13) |
C3—C4—H9 | 120.0 (15) | C12—C11—H5 | 118.2 (13) |
C5—C4—H9 | 119.4 (15) | C10—C12—C11 | 118.4 (2) |
C4—C5—C6 | 119.7 (3) | C10—C12—C8 | 122.1 (2) |
C4—C5—H8 | 124.0 (17) | C11—C12—C8 | 119.5 (2) |
C6—C5—H8 | 116.3 (17) | C7—N1—N2 | 120.0 (2) |
C5—C6—C1 | 120.8 (3) | C7—N1—H1 | 120.9 (14) |
C5—C6—H3 | 119.3 (13) | N2—N1—H1 | 118.9 (14) |
C1—C6—H3 | 119.9 (13) | C8—N2—N1 | 114.51 (19) |
O1—C7—N1 | 123.0 (2) | ||
C6—C1—C2—C3 | 1.3 (4) | C2—C1—C7—N1 | 149.0 (2) |
C7—C1—C2—C3 | 179.4 (2) | C11i—C10—C12—C11 | 0.4 (4) |
C1—C2—C3—C4 | −1.7 (4) | C11i—C10—C12—C8 | 179.2 (2) |
C2—C3—C4—C5 | 0.9 (4) | C10i—C11—C12—C10 | −0.4 (4) |
C3—C4—C5—C6 | 0.3 (4) | C10i—C11—C12—C8 | −179.3 (2) |
C4—C5—C6—C1 | −0.7 (4) | N2—C8—C12—C10 | −20.1 (3) |
C2—C1—C6—C5 | −0.1 (4) | N2—C8—C12—C11 | 158.7 (2) |
C7—C1—C6—C5 | −178.1 (2) | O1—C7—N1—N2 | −3.0 (3) |
C6—C1—C7—O1 | 147.0 (2) | C1—C7—N1—N2 | 177.04 (19) |
C2—C1—C7—O1 | −30.9 (3) | C12—C8—N2—N1 | 179.3 (2) |
C6—C1—C7—N1 | −33.0 (3) | C7—N1—N2—C8 | 168.7 (2) |
Symmetry code: (i) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1ii | 0.87 (2) | 2.19 (2) | 3.056 (3) | 171 (2) |
Symmetry code: (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C22H18N4O2 |
Mr | 370.40 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 30.569 (3), 5.1845 (3), 12.5191 (11) |
β (°) | 112.408 (7) |
V (Å3) | 1834.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.42 × 0.22 × 0.08 |
Data collection | |
Diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.976, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13265, 1905, 965 |
Rint | 0.105 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.078, 0.94 |
No. of reflections | 1905 |
No. of parameters | 163 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.11, −0.14 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.87 (2) | 2.19 (2) | 3.056 (3) | 171 (2) |
Symmetry code: (i) x, y−1, z. |
Footnotes
‡Additional correspondence author, e-mail: karimian.r@gmail.com.
Acknowledgements
The authors are grateful to the Islamic Azad University (Tabriz Branch), the University of Zanjan and Ondokuz Mayis University.
References
Bikas, R., Hosseini Monfared, H., Bijanzad, K., Koroglu, A. & Kazak, C. (2010b). Acta Cryst. E66, o2073. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bikas, R., Hosseini Monfared, H., Kazak, C., Arslan, N. B. & Bijanzad, K. (2010a). Acta Cryst. E66, o2015. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bikas, R., Hosseini Monfared, H., Lis, T. & Siczek, M. (2012). Acta Cryst. E68, o367–o368. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hosseini Monfared, H., Bikas, R. & Mayer, P. (2010a). Acta Cryst. E66, o236–o237. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hosseini Monfared, H., Bikas, R. & Mayer, P. (2010b). Inorg. Chim. Acta, 363, 2574–2583. Google Scholar
Savanini, L., Chiasserini, L., Gaeta, A. & Pellerano, C. (2002). Bioorg. Med. Chem. 10, 2193–2198. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar
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The design, synthesis, and characterization of metal complexes with Schiff-base ligands play a vital role in the coordination chemistry of transition metals. Hydrazones are a special group of compounds in the Schiff base family that are characterized by the presence of RR'C=N–N=C(O)R'' which two inter-linked nitrogen atoms (–N—N–) separate them from imines, oximes, etc. Hydrazone ligands derived from the condensation of acid hydrazides (R–CO–NH–NH2) with aromatic carbonyl compounds are important O, N-donor ligands. As biologically active compounds, hydrazones find application in the treatment of diseases such as tuberculosis, leprosy and mental disorder and also as anti-tumor agents. Hydrazone Schiff bases also have wide spread applications in fields such as coordination chemistry, bioinorganic chemistry , magnetics, electronics, nonlinear optics and fluorescent materials. Aroylhydrazone complexes also seem to be good candidates for catalytic oxidation studies because of their resistance to oxidation (Hosseini Monfared et al., 2010b). As part of our studies on the synthesis and characterization of hydrazone derivatives (Bikas et al., 2012, 2010a,b), we report here the crystal structure of (N',N''E,N',N''E)-N',N''-(1,4-phenylenebis(methan-1-yl-1-ylidene))dibenzohydrazide. The molecules of C22H18N4O2, lie across inversion centres and the asymmetric unit contains a half molecule (Fig. 1). The terminal benzene rings are parallel to each other and the distance of two planes which embrace these rings is 3.168 Å apart. The dihedral angle between the mean planes of the central and two terminal benzene rings is 66.03 (2)°. The molecule displays a trans configuration with respect to the C=N and N—N bonds. The packing diagram of the title compound is shown in Fig. 2. There are two strong intermolecular N—H···O hydrogen bonds in which the O atoms of the carbonyl groups (–C=O) act as hydrogen acceptors for the hydrogen of N—H and a one-dimensional chain is formed by these hydrogen bonds (Fig. 3).