organic compounds
(E)-4-Chloro-N′-(2,4,5-trifluorobenzylidene)benzohydrazide
aDepartment of Chemistry, Saranathan College of Engineering, Tiruchirappalli, Tamilnadu, India, bPG and Research Department of Chemistry, Periyar EVR College, Tiruchirappalli, Tamilnadu, India, and cDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203 Tamil Nadu, India
*Correspondence e-mail: swaroopapranav@gmail.com, phdguna@gmail.com
The title compound, C14H8ClF3N2O, is approximately planar, with a dihedral angle of 4.73 (6)° between the planes of the chlorophenyl and trifluorobenzylidene rings. In the crystal, molecules are stacked in a column along the b axis through π–π interactions [centroid–centroid distances = 3.7097 (12) and 3.7191 (12) Å].
Keywords: crystal structure; hydrazone derivative; π–π interactions.
CCDC reference: 1454889
Structure description
et al., 2013), anti-proliferative (Yadagiri et al., 2014), antiplatelet (Mashayekhi et al., 2013), anti-hepatitis (Şenkardeş et al., 2016) and anti-amoebic (Siddiqui et al., 2012) activities.
have continued to attract interest from researchers due to their medicinal applications. These derivatives exhibit antimicrobial (PieczonkaThe geometric parameters of the title molecule (Fig. 1) agree well with those reported for similar structures (Sreeja et al., 2013; Nair et al., 2012). The chlorophenyl ring makes a dihedral angle of 4.73 (6)° with the trifluorobenzylidene ring. In the crystal, the molecules are linked by π–π interactions [Cg1⋯Cg2i = 3. 7191 (12) Å and Cg1⋯Cg2ii = 3. 7096 (12) Å; symmetry codes: (i) 1 − x, −y, 2 − z; (ii) 1 − x, 1 − y, 2 − z]; Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively;
Synthesis and crystallization
To an ethanolic solution of 4-chlorobenzohydrazide (0.17 g, 0.001 mol), 2,4,5-trifluoro benzaldehyde (0.1 mL, 0.001 mol) and a few drops of conc. HCl were added. The reaction mixture was stirred well at room temperature for 30 min. The insoluble solid gradually generated was filtered and washed with petroleum benzine (60–80°C) and dried in a vacuum desiccator. The crude solid was recrystallized from DMSO solution (yield 98%).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 1Structural data
CCDC reference: 1454889
10.1107/S2414314616003047/is4002sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616003047/is4002Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616003047/is4002Isup3.cml
To an ethanolic solution of 4-chlorobenzohydrazide (0.17 g, 0.001 mol), 2,4,5-trifluoro benzaldehyde (0.1 ml, 0.001 mol) and a few drops of conc. HCl were added. The reaction mixture was stirred well at room temperature for 30 min. The insoluble solid gradually generated was filtered and washed with petroleum benzine (60–80°C) and dried in a vacuum desiccator. The crude solid was recrystallized from DMSO (yield 98%).
Hydrazones have continued to attract researchers due to their medicinal applications. These derivatives exhibit antimicrobial (Pieczonka et al., 2013), anti-proliferative (Yadagiri et al., 2014), antiplatelet (Mashayekhi et al., 2013), anti-hepatitis (Şenkardeş et al., 2016) and anti-amoebic (Siddiqui et al., 2012) activities.
The geometric parameters of the title molecule (Fig. 1) agree well with those reported for similar structures (Sreeja et al., 2013; Nair et al., 2012). The chlorophenyl ring makes a dihedral angle of 4.73 (6)° with the trifluorobenzylidene ring. The molecules are linked by π–π interactions [Cg1···Cg2i = 3. 7191 (12) Å and Cg1···Cg2ii = 3. 7096 (12) Å; symmetry codes: (i) 1 − x, −y, 2 − z; (ii) 1 − x, 1 − y, 2 − z]; Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms. |
C14H8ClF3N2O | Z = 2 |
Mr = 312.67 | F(000) = 316 |
Triclinic, P1 | Dx = 1.468 Mg m−3 |
a = 6.4998 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.4286 (2) Å | Cell parameters from 2925 reflections |
c = 14.8289 (4) Å | θ = 1.4–26.5° |
α = 84.859 (2)° | µ = 0.30 mm−1 |
β = 86.707 (2)° | T = 295 K |
γ = 83.313 (2)° | Block, colourless |
V = 707.47 (3) Å3 | 0.18 × 0.16 × 0.11 mm |
Bruker APEXII CCD diffractometer | 2925 independent reflections |
Radiation source: fine-focus sealed tube | 2162 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 0 pixels mm-1 | θmax = 26.5°, θmin = 1.4° |
ω and φ scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→9 |
Tmin = 0.948, Tmax = 0.968 | l = −18→18 |
10440 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0569P)2 + 0.2152P] where P = (Fo2 + 2Fc2)/3 |
2925 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C14H8ClF3N2O | γ = 83.313 (2)° |
Mr = 312.67 | V = 707.47 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.4998 (2) Å | Mo Kα radiation |
b = 7.4286 (2) Å | µ = 0.30 mm−1 |
c = 14.8289 (4) Å | T = 295 K |
α = 84.859 (2)° | 0.18 × 0.16 × 0.11 mm |
β = 86.707 (2)° |
Bruker APEXII CCD diffractometer | 2925 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2162 reflections with I > 2σ(I) |
Tmin = 0.948, Tmax = 0.968 | Rint = 0.025 |
10440 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.21 e Å−3 |
2925 reflections | Δρmin = −0.18 e Å−3 |
191 parameters |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.18109 (10) | 0.17309 (9) | 0.53712 (4) | 0.0773 (2) | |
F1 | 0.21764 (19) | 0.46649 (19) | 1.23486 (9) | 0.0731 (4) | |
F2 | 0.7236 (3) | 0.3478 (2) | 1.45102 (8) | 0.0871 (5) | |
N2 | 0.5848 (2) | 0.2425 (2) | 1.03868 (10) | 0.0488 (4) | |
N1 | 0.4890 (2) | 0.2335 (2) | 0.95876 (10) | 0.0489 (4) | |
H1 | 0.3580 | 0.2656 | 0.9555 | 0.059* | |
F3 | 0.9897 (2) | 0.19270 (19) | 1.32932 (8) | 0.0738 (4) | |
C4 | 0.4866 (3) | 0.1731 (2) | 0.80147 (11) | 0.0429 (4) | |
C5 | 0.2782 (3) | 0.2351 (3) | 0.79365 (12) | 0.0479 (4) | |
H5 | 0.2005 | 0.2772 | 0.8437 | 0.058* | |
C8 | 0.4666 (3) | 0.3037 (3) | 1.10238 (13) | 0.0497 (4) | |
H8 | 0.3278 | 0.3410 | 1.0918 | 0.060* | |
C2 | 0.5077 (3) | 0.1097 (3) | 0.64454 (13) | 0.0542 (5) | |
H2 | 0.5842 | 0.0676 | 0.5942 | 0.065* | |
C7 | 0.6013 (3) | 0.1743 (3) | 0.88617 (13) | 0.0494 (4) | |
C13 | 0.4658 (4) | 0.4083 (3) | 1.34516 (13) | 0.0578 (5) | |
H13 | 0.3728 | 0.4619 | 1.3876 | 0.069* | |
C6 | 0.1850 (3) | 0.2352 (3) | 0.71227 (12) | 0.0500 (5) | |
H6 | 0.0453 | 0.2771 | 0.7073 | 0.060* | |
O1 | 0.7870 (2) | 0.1260 (3) | 0.88799 (10) | 0.0826 (5) | |
C1 | 0.3014 (3) | 0.1725 (3) | 0.63871 (12) | 0.0499 (5) | |
C9 | 0.5423 (3) | 0.3175 (2) | 1.19213 (12) | 0.0455 (4) | |
C14 | 0.4111 (3) | 0.3957 (3) | 1.25786 (13) | 0.0511 (5) | |
C10 | 0.7425 (3) | 0.2490 (3) | 1.21677 (12) | 0.0483 (4) | |
H10 | 0.8368 | 0.1959 | 1.1747 | 0.058* | |
C3 | 0.5999 (3) | 0.1097 (3) | 0.72598 (13) | 0.0492 (4) | |
H3 | 0.7396 | 0.0670 | 0.7305 | 0.059* | |
C11 | 0.7985 (3) | 0.2609 (3) | 1.30357 (13) | 0.0519 (5) | |
C12 | 0.6613 (4) | 0.3393 (3) | 1.36670 (13) | 0.0574 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0880 (5) | 0.1003 (5) | 0.0470 (3) | −0.0101 (3) | −0.0175 (3) | −0.0158 (3) |
F1 | 0.0537 (7) | 0.0842 (9) | 0.0778 (8) | 0.0098 (6) | 0.0005 (6) | −0.0118 (7) |
F2 | 0.1174 (12) | 0.1016 (11) | 0.0447 (6) | −0.0074 (9) | −0.0183 (7) | −0.0162 (7) |
N2 | 0.0461 (9) | 0.0574 (10) | 0.0442 (8) | −0.0059 (7) | −0.0099 (7) | −0.0063 (7) |
N1 | 0.0406 (8) | 0.0628 (10) | 0.0442 (8) | −0.0019 (7) | −0.0091 (6) | −0.0106 (7) |
F3 | 0.0619 (8) | 0.0937 (10) | 0.0658 (7) | −0.0006 (7) | −0.0223 (6) | −0.0040 (7) |
C4 | 0.0417 (10) | 0.0439 (10) | 0.0433 (9) | −0.0049 (7) | −0.0022 (7) | −0.0047 (7) |
C5 | 0.0405 (10) | 0.0593 (11) | 0.0436 (9) | 0.0005 (8) | 0.0005 (7) | −0.0117 (8) |
C8 | 0.0459 (10) | 0.0553 (11) | 0.0490 (10) | −0.0060 (8) | −0.0069 (8) | −0.0070 (8) |
C2 | 0.0591 (12) | 0.0582 (12) | 0.0456 (10) | −0.0056 (9) | 0.0084 (9) | −0.0140 (9) |
C7 | 0.0414 (10) | 0.0577 (11) | 0.0488 (10) | −0.0044 (8) | −0.0040 (8) | −0.0041 (8) |
C13 | 0.0728 (14) | 0.0519 (12) | 0.0480 (10) | −0.0064 (10) | 0.0095 (10) | −0.0092 (9) |
C6 | 0.0412 (10) | 0.0596 (12) | 0.0494 (10) | 0.0000 (8) | −0.0062 (8) | −0.0098 (8) |
O1 | 0.0419 (8) | 0.1419 (16) | 0.0626 (9) | 0.0102 (9) | −0.0110 (7) | −0.0215 (9) |
C1 | 0.0579 (12) | 0.0519 (11) | 0.0417 (9) | −0.0089 (9) | −0.0056 (8) | −0.0082 (8) |
C9 | 0.0501 (10) | 0.0434 (10) | 0.0444 (9) | −0.0106 (8) | −0.0039 (8) | −0.0039 (8) |
C14 | 0.0507 (11) | 0.0472 (10) | 0.0549 (11) | −0.0041 (8) | 0.0001 (9) | −0.0045 (8) |
C10 | 0.0502 (11) | 0.0502 (11) | 0.0455 (9) | −0.0073 (8) | −0.0032 (8) | −0.0065 (8) |
C3 | 0.0414 (10) | 0.0524 (11) | 0.0533 (10) | −0.0012 (8) | 0.0014 (8) | −0.0092 (8) |
C11 | 0.0562 (12) | 0.0507 (11) | 0.0497 (10) | −0.0081 (9) | −0.0106 (9) | −0.0007 (8) |
C12 | 0.0786 (15) | 0.0541 (12) | 0.0417 (10) | −0.0123 (10) | −0.0078 (9) | −0.0064 (8) |
Cl1—C1 | 1.7363 (18) | C2—C1 | 1.372 (3) |
F1—C14 | 1.356 (2) | C2—C3 | 1.379 (3) |
F2—C12 | 1.345 (2) | C2—H2 | 0.9300 |
N2—C8 | 1.266 (2) | C7—O1 | 1.220 (2) |
N2—N1 | 1.380 (2) | C13—C12 | 1.358 (3) |
N1—C7 | 1.343 (2) | C13—C14 | 1.376 (3) |
N1—H1 | 0.8600 | C13—H13 | 0.9300 |
F3—C11 | 1.349 (2) | C6—C1 | 1.376 (3) |
C4—C5 | 1.387 (3) | C6—H6 | 0.9300 |
C4—C3 | 1.391 (2) | C9—C14 | 1.380 (3) |
C4—C7 | 1.498 (2) | C9—C10 | 1.397 (3) |
C5—C6 | 1.381 (2) | C10—C11 | 1.371 (2) |
C5—H5 | 0.9300 | C10—H10 | 0.9300 |
C8—C9 | 1.461 (2) | C3—H3 | 0.9300 |
C8—H8 | 0.9300 | C11—C12 | 1.375 (3) |
C8—N2—N1 | 114.85 (15) | C1—C6—H6 | 120.4 |
C7—N1—N2 | 119.69 (15) | C5—C6—H6 | 120.4 |
C7—N1—H1 | 120.2 | C2—C1—C6 | 121.46 (17) |
N2—N1—H1 | 120.2 | C2—C1—Cl1 | 120.08 (15) |
C5—C4—C3 | 118.83 (16) | C6—C1—Cl1 | 118.46 (15) |
C5—C4—C7 | 124.05 (16) | C14—C9—C10 | 117.17 (17) |
C3—C4—C7 | 117.10 (16) | C14—C9—C8 | 119.73 (17) |
C6—C5—C4 | 120.65 (16) | C10—C9—C8 | 123.07 (17) |
C6—C5—H5 | 119.7 | F1—C14—C13 | 117.91 (17) |
C4—C5—H5 | 119.7 | F1—C14—C9 | 118.15 (17) |
N2—C8—C9 | 121.75 (17) | C13—C14—C9 | 123.93 (18) |
N2—C8—H8 | 119.1 | C11—C10—C9 | 119.38 (18) |
C9—C8—H8 | 119.1 | C11—C10—H10 | 120.3 |
C1—C2—C3 | 119.12 (17) | C9—C10—H10 | 120.3 |
C1—C2—H2 | 120.4 | C2—C3—C4 | 120.77 (17) |
C3—C2—H2 | 120.4 | C2—C3—H3 | 119.6 |
O1—C7—N1 | 122.38 (17) | C4—C3—H3 | 119.6 |
O1—C7—C4 | 121.28 (17) | F3—C11—C10 | 120.38 (18) |
N1—C7—C4 | 116.33 (16) | F3—C11—C12 | 118.47 (17) |
C12—C13—C14 | 117.17 (18) | C10—C11—C12 | 121.14 (19) |
C12—C13—H13 | 121.4 | F2—C12—C13 | 119.85 (19) |
C14—C13—H13 | 121.4 | F2—C12—C11 | 118.9 (2) |
C1—C6—C5 | 119.17 (17) | C13—C12—C11 | 121.21 (18) |
C8—N2—N1—C7 | 178.48 (18) | C12—C13—C14—C9 | 0.1 (3) |
C3—C4—C5—C6 | −0.4 (3) | C10—C9—C14—F1 | 178.60 (17) |
C7—C4—C5—C6 | 177.82 (18) | C8—C9—C14—F1 | −3.5 (3) |
N1—N2—C8—C9 | 178.32 (16) | C10—C9—C14—C13 | −0.5 (3) |
N2—N1—C7—O1 | 0.6 (3) | C8—C9—C14—C13 | 177.41 (19) |
N2—N1—C7—C4 | −178.52 (15) | C14—C9—C10—C11 | 0.5 (3) |
C5—C4—C7—O1 | −176.5 (2) | C8—C9—C10—C11 | −177.34 (17) |
C3—C4—C7—O1 | 1.8 (3) | C1—C2—C3—C4 | −0.2 (3) |
C5—C4—C7—N1 | 2.7 (3) | C5—C4—C3—C2 | 0.5 (3) |
C3—C4—C7—N1 | −179.10 (17) | C7—C4—C3—C2 | −177.88 (18) |
C4—C5—C6—C1 | 0.1 (3) | C9—C10—C11—F3 | 178.76 (17) |
C3—C2—C1—C6 | −0.1 (3) | C9—C10—C11—C12 | −0.1 (3) |
C3—C2—C1—Cl1 | −179.75 (15) | C14—C13—C12—F2 | 180.00 (18) |
C5—C6—C1—C2 | 0.2 (3) | C14—C13—C12—C11 | 0.3 (3) |
C5—C6—C1—Cl1 | 179.82 (15) | F3—C11—C12—F2 | 1.1 (3) |
N2—C8—C9—C14 | 175.94 (18) | C10—C11—C12—F2 | 180.00 (18) |
N2—C8—C9—C10 | −6.3 (3) | F3—C11—C12—C13 | −179.17 (19) |
C12—C13—C14—F1 | −178.97 (18) | C10—C11—C12—C13 | −0.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C14H8ClF3N2O |
Mr | 312.67 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 6.4998 (2), 7.4286 (2), 14.8289 (4) |
α, β, γ (°) | 84.859 (2), 86.707 (2), 83.313 (2) |
V (Å3) | 707.47 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.18 × 0.16 × 0.11 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.948, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10440, 2925, 2162 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.120, 0.99 |
No. of reflections | 2925 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.18 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Acknowledgements
The authors express their thanks to the authorities of Saranathan College of Engineering, Tiruchirappalli, for providing laboratory facilities and the CAS in Crystallography and Biophysics, University of Madras, Chennai, for the data collection.
References
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Hydrazones have continued to attract researchers due to their medicinal applications. These derivatives exhibit antimicrobial (Pieczonka et al., 2013), anti-proliferative (Yadagiri et al., 2014), antiplatelet (Mashayekhi et al., 2013), anti-hepatitis (Şenkardeş et al., 2016) and antiamoebic (Siddiqui et al., 2012) activities.
The geometric parameters of the title molecule (Fig. 1) agree well with reported similar structure (Sreeja et al., 2013; Nair et al., 2012). The chlorophenyl ring makes a dihedral angles of 4.73 (6)° with the trifluorobenzylidene ring. The molecules are linked by π–π interactions [Cg1···Cg2i = 3. 7191 (12) Å and Cg1···Cg2ii = 3. 7096 (12) Å; symmetry codes: (i) 1 − x, −y, 2 − z; (ii) 1 − x, 1 − y, 2 − z]; Cg1 and Cg2 are the centroids of C1–C6 and C9–C14 rings, respectively