2,4-Di­chloro-6-{N-[2-(tri­fluoro­meth­yl)phen­yl]carboximido­yl}phenol

Xantini, Z.; Muller, A.; Lammertsma, K.

doi:10.1107/S2414314624010745

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 11| November 2024| x241074

https://doi.org/10.1107/S2414314624010745

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2,4-Dichloro-6-{N-[2-(trifluoromethyl)phenyl]carboximidoyl}phenol

Zizipho Xantini,^a ^* Alfred Muller ^a and Koop Lammertsma ^a

^aDepartment of Chemical Sciences, University of Johannesburg, 2006, South Africa
^*Correspondence e-mail: xantini.z@gmail.com

Edited by S. Parkin, University of Kentucky, USA (Received 23 September 2024; accepted 6 November 2024; online 14 November 2024)

The title compound, C₁₄H₈Cl₂F₃NO, was synthesized by the condensation between trifluoromethylaniline and dichlorosalicylaldehyde by nucleophilic addition, forming a hemiaminal, followed by a dehydration to generate an imine. The compound crystallizes in an orthorhombic Pbca (Z = 8) space group with a dihedral angle of 44.70 (5)° between the two aromatic rings. In the crystal, the molecules pack together to form a zigzag pattern along the c axis.

Keywords: crystal structure; Schiff base; trifluoromethylaniline; dichlorosalicylaldehyde; orthorhombic.

CCDC reference: 2400964

Structure description

Schiff base compounds have been synthesized since their discovery in 1864 (Tidwell, 2008 ), and have shown good viability as ligands in Schiff base–metal complexes (Ngan et al., 2011 ). Their versatility is attributed to the extensive range of potential ligand structures, which are dependent on the selection of aldehydes and amines (More et al., 2019 ) as starting reagents, with possibilities including bidentate, tridentate and tetradentate ligands. The synthesis typically involves condensation of primary amines and carbonyl compounds by nucleophilic addition, forming a hemiaminal, followed by a dehydration to generate an imine (Tovrog et al., 1976 ; Maihub et al., 2013 ; da Silva et al., 2011 ). The generated azomethine (C=N) dominates the properties of Schiff bases as the most important part in the Schiff base body (Maihub et al., 2013), and these have shown to be important for a wide range of applications in biological applications such as anti- bacterial and anti-fungal activities (Tovrog et al., 1976; Dhar & Taploo, 1982 ). As part of ongoing research in our group, we report here the synthesis and a crystal structure of a Schiff base ligand derived from dichlorosalicylaldehyde and 2-trifluoromethylaniline.

The title compound (Fig. 1) crystallizes in the Pbca (Z = 8) space group with molecules on general positions. The bond length for the azomethine group [N1—C8 = 1.274 (2) Å] suggest the presence of double-bond character as anticipated. The dihedral angle of 44.70 (5)° between the aromatic rings is predominantly attributed to the intramolecular O—H⋯N and intermolecular C—H⋯O hydrogen bonding (see Table 1). The molecules pack together to form a zigzag pattern along the c axis (see Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82 (2)	1.86 (2)	2.6111 (18)	152 (2)
C14—H14⋯O1ⁱ	0.93	2.67	3.515 (2)	151
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 1
An ellipsoid plot of the title compound with the atom-labelling scheme and displacement ellipsoids drawn at 50% probability level. H atoms are shown as small circles of arbitrary radius.

Figure 2
The crystal packing of the title compound, showing the layered packing arrangement, viewed along the c axis.

Synthesis and crystallization

2-Trifluoromethylaniline (1.0740 g, 20 mmol) and dichlorosalicylaldehyde (1.2662 g, 20 mmol) were refluxed in 10 ml of methanol overnight to give an orange solution. The volume of methanol was reduced, which resulted in an orange precipitate. Orange crystals were obtained by slow evaporation of a methanol solution. Yield 70.16%, 1.5578 g, 4.679 mmol; m.p. 140–143°C; IR (KBr, cm⁻¹): ν (Ar—OH) 3086; ν (C=N) 1612; ν (C—O) 1273. ¹H NMR (DMSO-d₆ in p.p.m, J in Hz): δ = 13.49 [1H (s), OH], 9.05 [1H (s), H5], 7.85 [2H (d, J = 10), H1, H2,], 7.81 [2H (s), H1,H8], 7.67 [1H, (d, J = 10), H7], 7.57 [1H, (t, J = 5)].

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₈Cl₂F₃NO
M_r	334.11
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	7.8436 (3), 13.8612 (4), 25.8433 (7)
V (Å³)	2809.73 (15)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.49
Crystal size (mm)	0.38 × 0.22 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.680, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	27956, 3353, 2679
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.111, 1.06
No. of reflections	3353
No. of parameters	194
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.36
Computer programs: APEX2 and SAINT (Bruker, 2010 ), SHELXT (Sheldrick, 2015a ), Mercury (Macrae et al., 2020 ), SHELXL (Sheldrick, 2015b ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2400964

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624010745/pk4045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624010745/pk4045Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624010745/pk4045Isup3.cml

checkCIF report

Computing details top

2,4-Dichloro-6-{N-[2-(trifluoromethyl)phenyl]carboximidoyl}phenol top

Crystal data top

C₁₄H₈Cl₂F₃NO	D_x = 1.580 Mg m⁻³
M_r = 334.11	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9920 reflections
a = 7.8436 (3) Å	θ = 3.0–27.7°
b = 13.8612 (4) Å	µ = 0.49 mm⁻¹
c = 25.8433 (7) Å	T = 293 K
V = 2809.73 (15) Å³	Block, yellow
Z = 8	0.38 × 0.22 × 0.14 mm
F(000) = 1344

Data collection top

Bruker APEXII CCD diffractometer	2679 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.040
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.9°, θ_min = 1.6°
T_min = 0.680, T_max = 0.746	h = −9→10
27956 measured reflections	k = −18→14
3353 independent reflections	l = −33→33

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0542P)² + 0.6574P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
3353 reflections	Δρ_max = 0.20 e Å⁻³
194 parameters	Δρ_min = −0.36 e Å⁻³

Special details top

Experimental. Crystallographic data was collected on a Bruker DUO APEX II diffractometer (Bruker, 2010). The intensity data were obtained and adjusted using the SAINT software (Bruker, 2010). The correction of the collected intensities for absorption was done using SADABS (Krause et al., 2015). The structure was solved using SHELXT (Sheldrick, 2015a). The refinement of the structure was done using SHELXL (Sheldrick, 2015b) with the X-SEED (Barbour, 2020) software interface using anisotropic models for non-hydrogen atoms. Mercury (Macrae et al., 2020) was used to prepare the figures for publication.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.22744 (7)	0.45151 (3)	0.52669 (2)	0.07023 (17)
Cl2	0.51694 (7)	0.71474 (4)	0.65169 (2)	0.07656 (18)
O1	0.30841 (17)	0.58814 (9)	0.44463 (5)	0.0565 (3)
N1	0.43077 (18)	0.75064 (9)	0.40953 (5)	0.0490 (3)
F1	0.6420 (3)	0.65886 (12)	0.27056 (5)	0.1294 (7)
C1	0.5703 (3)	0.67847 (16)	0.31575 (7)	0.0737 (6)
C2	0.5393 (3)	0.78362 (13)	0.32338 (7)	0.0587 (4)
C3	0.4678 (2)	0.81737 (11)	0.36918 (6)	0.0508 (4)
C4	0.4317 (3)	0.91504 (13)	0.37471 (8)	0.0655 (5)
H4	0.380492	0.937641	0.404823	0.079*
C5	0.4722 (3)	0.97866 (16)	0.33510 (10)	0.0846 (7)
H5	0.447098	1.043908	0.338600	0.101*
C6	0.5491 (4)	0.94580 (17)	0.29087 (9)	0.0917 (8)
H6	0.578551	0.989010	0.264838	0.110*
C7	0.5829 (3)	0.84888 (17)	0.28488 (8)	0.0796 (6)
H7	0.635311	0.827058	0.254796	0.096*
C8	0.4679 (2)	0.77357 (11)	0.45590 (6)	0.0476 (3)
H8	0.518662	0.833044	0.462209	0.057*
C9	0.43343 (19)	0.70977 (10)	0.49926 (6)	0.0448 (3)
C10	0.35574 (19)	0.61936 (10)	0.49151 (6)	0.0459 (3)
C11	0.3277 (2)	0.56153 (11)	0.53473 (7)	0.0509 (4)
C12	0.3767 (2)	0.58980 (12)	0.58379 (7)	0.0556 (4)
H12	0.357636	0.549712	0.612062	0.067*
F2	0.4265 (2)	0.62654 (10)	0.31795 (6)	0.1064 (5)
F3	0.6717 (2)	0.63993 (9)	0.35177 (5)	0.0902 (4)
C14	0.4823 (2)	0.73832 (12)	0.54898 (6)	0.0494 (4)
H14	0.533728	0.798015	0.554050	0.059*
C13	0.4542 (2)	0.67828 (13)	0.59027 (6)	0.0535 (4)
H1	0.340 (3)	0.6303 (17)	0.4244 (9)	0.076 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0718 (3)	0.0469 (2)	0.0920 (4)	−0.00955 (19)	0.0038 (2)	0.0095 (2)
Cl2	0.0816 (4)	0.1008 (4)	0.0473 (3)	0.0027 (3)	−0.0062 (2)	−0.0007 (2)
O1	0.0660 (7)	0.0459 (6)	0.0575 (7)	−0.0080 (6)	−0.0031 (6)	−0.0028 (5)
N1	0.0545 (8)	0.0446 (6)	0.0480 (7)	−0.0019 (6)	−0.0011 (6)	0.0014 (5)
F1	0.211 (2)	0.1037 (11)	0.0738 (9)	0.0138 (13)	0.0464 (11)	−0.0189 (8)
C1	0.0995 (16)	0.0697 (12)	0.0520 (10)	−0.0034 (12)	0.0069 (10)	−0.0094 (9)
C2	0.0709 (11)	0.0610 (10)	0.0441 (9)	−0.0053 (9)	−0.0093 (8)	0.0030 (7)
C3	0.0542 (9)	0.0494 (8)	0.0488 (9)	−0.0043 (7)	−0.0089 (7)	0.0042 (7)
C4	0.0782 (12)	0.0506 (9)	0.0677 (11)	0.0024 (9)	−0.0076 (9)	0.0051 (8)
C5	0.1106 (18)	0.0551 (10)	0.0880 (16)	0.0004 (12)	−0.0164 (14)	0.0210 (10)
C6	0.125 (2)	0.0807 (15)	0.0689 (13)	−0.0138 (14)	−0.0142 (14)	0.0330 (12)
C7	0.1047 (17)	0.0875 (15)	0.0466 (10)	−0.0091 (13)	−0.0052 (10)	0.0140 (9)
C8	0.0481 (8)	0.0420 (7)	0.0527 (9)	−0.0033 (6)	−0.0003 (7)	−0.0001 (6)
C9	0.0433 (7)	0.0433 (7)	0.0479 (8)	0.0015 (6)	0.0012 (6)	0.0009 (6)
C10	0.0429 (8)	0.0419 (7)	0.0529 (8)	0.0041 (6)	0.0009 (6)	−0.0009 (6)
C11	0.0454 (8)	0.0411 (7)	0.0661 (10)	0.0025 (6)	0.0051 (7)	0.0070 (7)
C12	0.0518 (9)	0.0575 (9)	0.0574 (9)	0.0073 (7)	0.0062 (7)	0.0145 (7)
F2	0.1260 (13)	0.0786 (8)	0.1145 (12)	−0.0282 (8)	−0.0055 (9)	−0.0313 (8)
F3	0.1110 (11)	0.0675 (7)	0.0922 (9)	0.0197 (7)	0.0019 (8)	0.0058 (6)
C14	0.0476 (8)	0.0490 (8)	0.0514 (9)	0.0005 (7)	−0.0007 (7)	−0.0004 (7)
C13	0.0509 (9)	0.0639 (10)	0.0457 (8)	0.0070 (7)	−0.0002 (7)	0.0011 (7)

Geometric parameters (Å, º) top

Cl1—C11	1.7286 (16)	C5—C6	1.370 (4)
Cl2—C13	1.7369 (18)	C5—H5	0.9300
O1—C10	1.3389 (19)	C6—C7	1.378 (3)
O1—H1	0.82 (2)	C6—H6	0.9300
N1—C8	1.274 (2)	C7—H7	0.9300
N1—C3	1.424 (2)	C8—C9	1.453 (2)
F1—C1	1.324 (2)	C8—H8	0.9300
C1—F3	1.336 (3)	C9—C14	1.398 (2)
C1—F2	1.339 (3)	C9—C10	1.408 (2)
C1—C2	1.491 (3)	C10—C11	1.392 (2)
C2—C7	1.388 (3)	C11—C12	1.382 (3)
C2—C3	1.391 (3)	C12—C13	1.379 (3)
C3—C4	1.391 (2)	C12—H12	0.9300
C4—C5	1.388 (3)	C14—C13	1.371 (2)
C4—H4	0.9300	C14—H14	0.9300

C10—O1—H1	105.2 (16)	C6—C7—H7	119.7
C8—N1—C3	118.70 (14)	C2—C7—H7	119.7
F1—C1—F3	106.3 (2)	N1—C8—C9	122.10 (14)
F1—C1—F2	106.53 (19)	N1—C8—H8	119.0
F3—C1—F2	104.88 (18)	C9—C8—H8	119.0
F1—C1—C2	112.73 (18)	C14—C9—C10	120.08 (14)
F3—C1—C2	113.33 (17)	C14—C9—C8	119.06 (14)
F2—C1—C2	112.5 (2)	C10—C9—C8	120.84 (14)
C7—C2—C3	119.36 (18)	O1—C10—C11	119.74 (14)
C7—C2—C1	120.17 (18)	O1—C10—C9	122.44 (14)
C3—C2—C1	120.47 (16)	C11—C10—C9	117.82 (14)
C4—C3—C2	119.81 (16)	C12—C11—C10	121.95 (15)
C4—C3—N1	121.04 (16)	C12—C11—Cl1	119.14 (13)
C2—C3—N1	119.14 (15)	C10—C11—Cl1	118.90 (13)
C5—C4—C3	119.7 (2)	C13—C12—C11	119.09 (15)
C5—C4—H4	120.1	C13—C12—H12	120.5
C3—C4—H4	120.1	C11—C12—H12	120.5
C6—C5—C4	120.3 (2)	C13—C14—C9	119.98 (15)
C6—C5—H5	119.8	C13—C14—H14	120.0
C4—C5—H5	119.8	C9—C14—H14	120.0
C5—C6—C7	120.2 (2)	C14—C13—C12	121.07 (16)
C5—C6—H6	119.9	C14—C13—Cl2	119.29 (14)
C7—C6—H6	119.9	C12—C13—Cl2	119.64 (13)
C6—C7—C2	120.5 (2)

F1—C1—C2—C7	0.8 (3)	C3—N1—C8—C9	179.68 (14)
F3—C1—C2—C7	121.5 (2)	N1—C8—C9—C14	178.07 (15)
F2—C1—C2—C7	−119.7 (2)	N1—C8—C9—C10	−0.4 (2)
F1—C1—C2—C3	−178.7 (2)	C14—C9—C10—O1	−179.21 (14)
F3—C1—C2—C3	−58.0 (3)	C8—C9—C10—O1	−0.7 (2)
F2—C1—C2—C3	60.8 (2)	C14—C9—C10—C11	1.0 (2)
C7—C2—C3—C4	3.8 (3)	C8—C9—C10—C11	179.47 (14)
C1—C2—C3—C4	−176.72 (19)	O1—C10—C11—C12	178.95 (15)
C7—C2—C3—N1	−177.07 (18)	C9—C10—C11—C12	−1.3 (2)
C1—C2—C3—N1	2.5 (3)	O1—C10—C11—Cl1	−1.5 (2)
C8—N1—C3—C4	−44.0 (2)	C9—C10—C11—Cl1	178.29 (12)
C8—N1—C3—C2	136.83 (17)	C10—C11—C12—C13	0.6 (2)
C2—C3—C4—C5	−2.1 (3)	Cl1—C11—C12—C13	−178.95 (13)
N1—C3—C4—C5	178.77 (18)	C10—C9—C14—C13	−0.1 (2)
C3—C4—C5—C6	−0.6 (4)	C8—C9—C14—C13	−178.60 (15)
C4—C5—C6—C7	1.6 (4)	C9—C14—C13—C12	−0.6 (3)
C5—C6—C7—C2	0.1 (4)	C9—C14—C13—Cl2	179.61 (12)
C3—C2—C7—C6	−2.8 (3)	C11—C12—C13—C14	0.4 (3)
C1—C2—C7—C6	177.7 (2)	C11—C12—C13—Cl2	−179.85 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82 (2)	1.86 (2)	2.6111 (18)	152 (2)
C14—H14···O1ⁱ	0.93	2.67	3.515 (2)	151

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Acknowledgements

Special thanks to Dr B. Vatsha at the Department of Chemical Sciences, University of Johannesburg, South Africa, for collecting the data.

Funding information

Funding for this research was provided by: South African National Research Foundation. (grant No. 120842).

References

Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dhar, D. N. & Taploo, C. L. (1982). J. Sci. Res. 41, 501–506. CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Maihub, A. A., El-ajaily, M. M., Abou-Krisha, M. M., Etorki, M. A. & Alassbaly, F. S. (2013). J. Chem. Pharm. Res. 12, 933–938. Google Scholar
More, M. S., Joshi, P. G., Mishra, Y. K. & Khanna, P. K. (2019). Mater. Today Chem., 14, 100195. CrossRef PubMed Google Scholar
Ngan, N. K., Lo, K. M. & Wong, C. S. R. (2011). Polyhedron, 30, 2922–2932. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Silva, C. M. da, da Silva, D. L., Modolo, L. V., Alves, R. B., de Resende, M. A. & Martins, C. V. B. de Fátima (2011). J. Adv. Res. 2, 1–8. Google Scholar
Tidwell, T. T. (2008). Angew. Chem. Int. Ed. 47, 1016–1020. Web of Science CrossRef CAS Google Scholar
Tovrog, B. S., Kitko, D. J. & Drago, R. S. (1976). J. Am. Chem. Soc. 98, 5144–5153. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar