Crystallographic and spectroscopic character­ization of 4-nitro-2-(tri­fluoro­meth­yl)benzoic acid and 4-nitro-3-(tri­fluoro­meth­yl)benzoic acid

Diehl III, G.L.; Je, L.; Tanski, J.M.

doi:10.1107/S2056989019003979

research communications

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ISSN: 2056-9890

Volume 75| Part 4| April 2019| Pages 524-528

https://doi.org/10.1107/S2056989019003979

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Crystallographic and spectroscopic characterization of 4-nitro-2-(trifluoromethyl)benzoic acid and 4-nitro-3-(trifluoromethyl)benzoic acid

George L. Diehl III,^a Lisa Je ^a and Joseph M. Tanski ^a ^*

^aDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA
^*Correspondence e-mail: jotanski@vassar.edu

Edited by S. Parkin, University of Kentucky, USA (Received 21 March 2019; accepted 22 March 2019; online 29 March 2019)

The title compounds, both C₈H₄F₃NO₄, represent two isomers of nitro trifluoromethyl benzoic acid. The compounds each contain a nitro functionality para to the carboxylic acid group, with the trifluoromethyl substituent ortho to the acid group in the 2-isomer and ortho to the nitro group in the 3-isomer. The regiochemistry with respect to the trifluoromethyl group results in steric interactions that rotate the carboxylic acid group or the nitro group out of the aromatic plane in the 2- and 3-isomer, respectively. Each molecule engages in intermolecular hydrogen bonding, forming head-to-tail dimers with graph-set notation R₂²(8) and donor–acceptor hydrogen-bonding distances of 2.7042 (14) Å in the 2-isomer and 2.6337 (16) in the 3-isomer. Recrystallization attempts did not yield untwinned crystals.

Keywords: crystal structure; hydrogen bonding; benzoic acid derivatives; trifluoromethyl group.

CCDC references: 1905077; 1905076

1. Chemical context

The title compounds, 4-nitro-2-(trifluoromethyl)benzoic acid (I) and 4-nitro-3-(trifluoromethyl)benzoic acid (II), are tri-substituted aromatic compounds featuring a carboxylic acid, a nitro group and a trifluoromethyl group. Although all ten isomers of nitro trifluoromethyl benzoic acid are available commercially, none of their crystal structures have been reported. 4-Nitro-2-(trifluoromethyl)benzoic acid (I) may be synthesized from 2-(trifluoromethyl)benzoic acid by treating it with concentrated sulfuric acid, stirring, and adding fuming nitric acid dropwise (Kompella et al., 2017 ). 4-Nitro-2-(trifluoromethyl)benzoic acid (I) has been used in the syntheses of potential pharmaceuticals, for example in anti-tumor pyridinone (Cheung et al., 2017 ) and urea derivatives (Nishio et al., 2017 ). 4-Nitro-3-(trifluoromethyl)benzoic acid (II) was first reported in 1951 after being prepared from the corresponding nitrile (Caldwell & Sayin, 1951 ). The compound has recently been used for the synthesis of glutamate receptor antagonists (Selvam et al., 2018 ) that have potential as therapies for diseases such as Parkinson's.

2. Structural commentary

4-Nitro-2-(trifluoromethyl)benzoic acid, (I) (Fig. 1), and 4-nitro-3-(trifluoromethyl)benzoic acid, (II) (Fig. 2), exhibit similar metrical parameters. The aromatic nitro bond length C4—N1 of 1.4718 (16) Å in (I) and 1.4751 (19) in (II) are similar, as are the aromatic trifluoromethyl bond lengths C2—C8 of 1.5114 (17) Å in (I) and C3—C8 of 1.508 (2) Å in (II). The nitro N—O distances lie between 1.2154 (19) and 1.2271 (14) Å; average 1.224 (6) Å. Whereas the carboxylic acid group in (I) is not significantly disordered, with an O1—C7 carbonyl bond length of 1.219 (2) Å and an O2—C7 acid bond length of 1.3139 (16) Å, the carboxylic acid group in (II) exhibits some twofold disorder, with an O1—C7 bond length of 1.2528 (18) Å and O2—C7 acid bond length of 1.281 (2) Å.

Figure 1
A view of 4-nitro-2-(trifluoromethyl)benzoic acid (I)

with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level.

Figure 2
A view of 4-nitro-3-(trifluoromethyl)benzoic acid (II)

with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level.

A notable difference in the molecular structures of the title compounds is the influence of the trifluoromethyl substituent on the co-planarity of the carboxylic acid and nitro groups with the aromatic ring plane (Fig. 3). In 4-nitro-2-(trifluoromethyl)benzoic acid (I), the trifluoromethyl group ortho to the carboxylic acid moiety rotates it out of the plane of the aromatic ring, with a plane-to-plane angle of 47.2 (1)°, whereas the nitro group is almost co-planar with the aromatic ring, with an angle of 2.0 (1)°. Conversely, in 4-nitro-3-(trifluoromethyl)benzoic acid (II), the trifluoromethyl group ortho to the nitro moiety rotates it out of the plane of the aromatic ring, with a plane-to-plane angle of 51.3 (1)°, whereas the carboxylic acid group is closer to co-planar with the aromatic ring, with an angle of 4.9 (2)°.

Figure 3
Side-by-side views of 4-nitro-2-(trifluoromethyl)benzoic acid (I)

(left) and 4-nitro-3-(trifluoromethyl)benzoic acid (II)

indicating the rotation of the carboxyl and nitro groups out of the mean plane of the aromatic ring.

3. Supramolecular features

The molecules of the title compounds pack together in the solid state with hydrogen bonding between the carboxylic acid hydrogen atom and the carbonyl oxygen atom of the symmetry-related carboxyl group in a neighboring molecule, forming a dimer with graph-set notation R₂²(8). This centrosymmetric pairwise hydrogen-bonding dimer formation results in short hydrogen-bonding distances of 2.7042 (14) Å in (I) (Fig. 4, Table 1) and 2.6337 (16) in (II) (Fig. 5, Table 2).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.85 (1)	1.86 (2)	2.7042 (14)	175 (2)
Symmetry code: (i) -x+1, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.83 (2)	1.82 (2)	2.6337 (16)	168 (2)
Symmetry code: (i) -x, -y+1, -z.

Figure 4
A view of the intermolecular hydrogen bonding in 4-nitro-2-(trifluoromethyl)benzoic acid (I)

. [Symmetry code: (i) −x + 1, −y + 1, −z.]

Figure 5
A view of the intermolecular hydrogen bonding in 4-nitro-3-(trifluoromethyl)benzoic acid (II)

. [Symmetry code: (i) −x, −y + 1, −z.]

The molecular packing in the unit cell of 4-nitro-2-(trifluoromethyl)benzoic acid (I) (Fig. 6) reveals a dimerized face-to-face geometrical arrangement of the aromatic rings related by inversion, with a ring centroid-to-centroid distance of 3.907 (1) Å, a centroid-to-plane distance of 3.820 (1) Å, and a ring-offset slippage of 0.822 (2) Å. An intermolecular fluorine–fluorine interaction is also observed with a length of 2.927 (1) Å that is similar to the sum of the van der Waals radii (2.94 Å; Bondi, 1964 ). The hydrogen bonded dimers of 4-nitro-3-(trifluoromethyl)benzoic acid (II) pack together in a similar way, but with a longer fluorine–fluorine contact [2.975 (2) Å] and a highly offset face-to-face geometric arrangement of the aromatic rings characterized by a large ring-offset slippage of 1.733 (2) Å such that the aromatic rings are barely overlapped (Fig. 7).

Figure 6
A view of the packing in 4-nitro-2-(trifluoromethyl)benzoic acid (I)

with a double-dashed line indicating the F⋯F interaction and a thick solid line indicating a centroid-to-centroid interaction. [Symmetry code: (i) −x + $[{3\over 2}]$ , y, z + $[{1\over 2}]$ .]

Figure 7
A view of the packing in 4-nitro-3-(trifluoromethyl)benzoic acid (II)

with a double-dashed line indicating the F⋯F interaction and a thick solid line indicating a centroid-to-centroid interaction. [Symmetry code: (i) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z.]

4. Database survey

The Cambridge Structural Database (Groom et al., 2016 ) contains no isomers of nitro trifluoromethyl benzoic acid. A related derivative of 4-nitro-3-(trifluoromethyl)benzoic acid (II) is 3-methyl-4-nitrobenzoic acid (TOYGIZ), which exhibits a similar hydrogen-bonding motif and hydrogen-bonding distance of 2.617 Å (Saha et al., 2015 ). As with (II), the methyl group ortho to the nitro moiety in TOYGIZ rotates it out of the plane of the aromatic ring whereas the carboxylic acid group is closer to co-planar with the aromatic ring.

5. Synthesis and crystallization

4-Nitro-2-(trifluoromethyl)benzoic acid (I) (97%) was purchased from Alfa Aesar and 4-nitro-3-(trifluoromethyl)benzoic acid (II) (97%) were purchased from Aldrich Chemical Company. (I) was recrystallized from tetrahydrofuran and (II) was used as received.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms on carbon were included in calculated positions and refined using a riding model with C—H = 0.95 and U_iso(H) = 1.2U_eq(C) of the aryl C-atoms the hydrogens are riding on. The positions of the carboxylic acid hydrogen atoms were found in the difference map and the atoms refined semi-freely using a distance restraint d(O—H) = 0.84 Å, and U_iso(H) = 1.2U_eq(O). 4-Nitro-3-(trifluoromethyl)benzoic acid (II) was found to be multiply non-merohedrally twinned. Recrystallization attempts did not yield untwinned crystals. Three components were integrated with SAINT using the multiple-component orientation matrix produced by CELL_NOW (Sheldrick, 2003 ), and the data were absorption corrected and scaled with TWINABS (Sheldrick, 2008a ). The initial solution was found and refined with merged and roughly detwinned HKLF 4 format data before final refinement against HKLF5 format data constructed from all observations involving domain 1 only. The twin ratio (SHELXL BASF parameters) refined to 0.0961 (3) and 0.0326 (2).

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₈H₄F₃NO₄	C₈H₄F₃NO₄
M_r	235.12	235.12
Crystal system, space group	Orthorhombic, Pccn	Monoclinic, P2₁/n
Temperature (K)	125	125
a, b, c (Å)	12.1612 (17), 14.847 (2), 9.8265 (14)	6.8986 (8), 17.240 (2), 7.6912 (9)
α, β, γ (°)	90, 90, 90	90, 107.685 (2), 90
V (Å³)	1774.2 (4)	871.50 (18)
Z	8	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.18	0.18
Crystal size (mm)	0.24 × 0.24 × 0.15	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )	Multi-scan (TWINABS; Sheldrick, 2008a)
T_min, T_max	0.86, 0.97	0.89, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	40170, 2727, 2064	4385, 2665, 2116
R_int	0.050	0.071
(sin θ/λ)_max (Å⁻¹)	0.716	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.04	0.048, 0.150, 1.05
No. of reflections	2727	2873
No. of parameters	148	150
No. of restraints	1	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.24	0.50, −0.36
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008b ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2008 ).

7. Analytical data

(I) ¹H NMR (Bruker Avance III HD 400 MHz, DMSO d₆): δ 8.07 (d, 1 H, C_arylH, J_ortho = 8.4 Hz), 8.50 (d, 1 H, C_arylH, J_meta = 2.2 Hz), 8.56 (dd, 1 H, C_arylH, J_ortho = 8.4 Hz, J_meta = 2.2 Hz), 14.28 (br s, 1 H, OH). ¹³C NMR (¹³C{¹H}, 100.6 MHz, DMSO d₆): δ 121.76 (q, C_arylH, J_C-F = 5.4 Hz), 122.31 (q, CF₃, J_C-F = 274 Hz), 127.20 (q, C_arylCF₃, J_C-F = 33.5 Hz), 127.64 (s, C_arylH), 131.35 (s, C_arylH), 137.86 (s, C_arylCOOH), 148.27 (s, C_arylNO₂), 166.44 (s, COOH). IR (Thermo Nicolet iS50, ATR, cm⁻¹): 3133 (s br, O—H str), 3096 (s, C_aryl-H str), 2922 (s), 2660 (m), 2531 (m), 1723 (s, C=O str), 1618 (s), 1540 (s), 1498 (m), 1407 (s), 1357 (s), 1317 (s), 1294 (s), 1268 (s), 1177 (m), 1153 (s), 1115 (s), 1048 (s), 920 (s), 899 (m), 861 (m), 803 (s), 769 (w), 742 (m), 700 (m), 656 (m), 563 (m), 503 (m). GC–MS (Agilent Technologies 7890A GC/5975C MS): M⁺ = 249 amu, corresponding to the methyl ester of (I), prepared from the parent carboxylic acid using a literature procedure (Di Raddo, 1993 ).

(II) ¹H NMR (Bruker Avance III HD 400 MHz, DMSO d₆): δ 8.28 (d, 1H, C_arylH, J_ortho = 8.4 Hz), 8.36 (d, 1H, C_arylH, J_meta = 1.6 Hz), 8.43 (dd, 1 H, C_arylH, J_ortho = 8.0 Hz, J_meta = 1.8 Hz), 14.06 (br s, 1H, OH). ¹³C NMR (¹³C{¹H}, 100.6 MHz, DMSO d₆): δ 121.53 (q, C_arylCF₃, J_C-F = 33.9 Hz), 121.64 (q, CF₃, J_C-F = 273 Hz), 126.0 (s, C_arylH), 128.30 (q, C_arylH, J_C-F = 5.2 Hz), 135.02 (s, C_arylH), 135.13 (s, C_arylCOOH), 149.38 (s, C_aryl NO₂), 164.48 (s, COOH). ¹⁹F NMR (¹⁹F{¹H}, 376.5 MHz, DMSO d₆): −59.24 (s, 3F, CF₃). IR (Thermo Scientific iS50, ATR, cm⁻¹): 3104 (m br, O-H str), 3067 (m, C_aryl-H str), 2848 (m), 2646 (m), 2575 (m), 1700 (s, C=O str), 1618 (m), 1598 (m), 1548 (s), 1438 (m), 1409 (m), 1363 (m), 1313 (m), 1267 (s) 1176 (m), 1163 (s), 1140 (s), 1125 (s), 1049 (m), 912 (m), 889 (m), 827 (m), 779 (m), 766 (m), 747 (m), 721 (w), 702 (m), 654 (m), 616 (w), 545 (m), 506 (m), 419 (m). GC–MS (Agilent Technologies 7890A GC/5975C MS): M⁺ = 249 amu, corresponding to the methyl ester of (II), prepared from the parent carboxylic acid using a literature procedure (Raddo, 1993).

Supporting information

CCDC references: 1905077; 1905076

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989019003979/pk2616sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019003979/pk2616Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019003979/pk2616IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019003979/pk2616Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019003979/pk2616IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

4-Nitro-2-(trifluoromethyl)benzoic acid (I) top

Crystal data top

C₈H₄F₃NO₄	D_x = 1.760 Mg m⁻³
M_r = 235.12	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 7558 reflections
a = 12.1612 (17) Å	θ = 2.2–30.2°
b = 14.847 (2) Å	µ = 0.18 mm⁻¹
c = 9.8265 (14) Å	T = 125 K
V = 1774.2 (4) Å³	Block, colourless
Z = 8	0.24 × 0.24 × 0.15 mm
F(000) = 944

Data collection top

Bruker APEXII CCD diffractometer	2727 independent reflections
Radiation source: fine-focus sealed tube	2064 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.6°, θ_min = 2.2°
φ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −21→21
T_min = 0.86, T_max = 0.97	l = −14→14
40170 measured reflections

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0543P)² + 0.5851P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2727 reflections	Δρ_max = 0.46 e Å⁻³
148 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

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
F1	0.73315 (7)	0.52183 (6)	0.34266 (10)	0.0370 (2)
F2	0.76500 (7)	0.65169 (7)	0.42859 (9)	0.0367 (2)
F3	0.70454 (7)	0.64131 (6)	0.22366 (9)	0.0347 (2)
O1	0.55716 (9)	0.49377 (7)	0.14946 (10)	0.0306 (2)
O2	0.43545 (9)	0.59970 (7)	0.08655 (10)	0.0289 (2)
H2	0.4403 (15)	0.5727 (12)	0.0103 (16)	0.035*
O3	0.52250 (8)	0.69576 (7)	0.79079 (10)	0.0285 (2)
O4	0.34577 (8)	0.69044 (7)	0.76367 (10)	0.0284 (2)
N1	0.44022 (9)	0.68191 (7)	0.72167 (11)	0.0211 (2)
C1	0.48757 (10)	0.59507 (8)	0.31669 (12)	0.0198 (2)
C2	0.57846 (10)	0.61229 (8)	0.40071 (12)	0.0192 (2)
C3	0.56260 (10)	0.64170 (8)	0.53324 (13)	0.0193 (2)
H3A	0.623518	0.65393	0.590881	0.023*
C4	0.45566 (10)	0.65286 (8)	0.57974 (12)	0.0187 (2)
C5	0.36455 (10)	0.63879 (8)	0.49877 (13)	0.0213 (2)
H5A	0.29241	0.648629	0.53275	0.026*
C6	0.38158 (10)	0.60982 (9)	0.36620 (13)	0.0222 (3)
H6A	0.320197	0.599895	0.308322	0.027*
C7	0.49830 (11)	0.55800 (9)	0.17519 (13)	0.0225 (3)
C8	0.69530 (11)	0.60658 (9)	0.34899 (13)	0.0247 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0285 (5)	0.0381 (5)	0.0443 (5)	0.0138 (4)	0.0073 (4)	−0.0025 (4)
F2	0.0182 (4)	0.0570 (6)	0.0350 (5)	−0.0067 (4)	0.0034 (3)	−0.0103 (4)
F3	0.0296 (4)	0.0487 (6)	0.0259 (4)	−0.0011 (4)	0.0093 (3)	0.0043 (4)
O1	0.0402 (6)	0.0281 (5)	0.0235 (5)	0.0113 (4)	−0.0049 (4)	−0.0053 (4)
O2	0.0364 (5)	0.0316 (5)	0.0188 (4)	0.0093 (4)	−0.0041 (4)	−0.0024 (4)
O3	0.0230 (5)	0.0384 (6)	0.0241 (5)	−0.0012 (4)	−0.0023 (4)	−0.0077 (4)
O4	0.0206 (4)	0.0340 (5)	0.0307 (5)	0.0012 (4)	0.0075 (4)	−0.0080 (4)
N1	0.0194 (5)	0.0214 (5)	0.0225 (5)	0.0008 (4)	0.0020 (4)	−0.0030 (4)
C1	0.0220 (6)	0.0180 (5)	0.0195 (5)	0.0006 (4)	−0.0006 (4)	0.0002 (4)
C2	0.0170 (5)	0.0202 (6)	0.0203 (6)	0.0015 (4)	0.0021 (4)	0.0011 (4)
C3	0.0160 (5)	0.0213 (6)	0.0206 (5)	0.0003 (4)	−0.0014 (4)	−0.0002 (4)
C4	0.0178 (5)	0.0185 (5)	0.0197 (5)	0.0008 (4)	0.0013 (4)	−0.0011 (4)
C5	0.0158 (5)	0.0223 (6)	0.0259 (6)	0.0008 (4)	0.0002 (4)	−0.0013 (5)
C6	0.0191 (5)	0.0230 (6)	0.0247 (6)	−0.0006 (4)	−0.0042 (5)	−0.0019 (5)
C7	0.0254 (6)	0.0204 (6)	0.0218 (6)	−0.0007 (5)	−0.0014 (5)	−0.0001 (4)
C8	0.0203 (6)	0.0312 (7)	0.0224 (6)	0.0017 (5)	0.0031 (5)	−0.0012 (5)

Geometric parameters (Å, º) top

F1—C8	1.3413 (16)	C1—C2	1.4031 (17)
F2—C8	1.3337 (16)	C1—C7	1.5011 (17)
F3—C8	1.3399 (16)	C2—C3	1.3871 (17)
O1—C7	1.2188 (16)	C2—C8	1.5114 (17)
O2—C7	1.3139 (16)	C3—C4	1.3884 (16)
O2—H2	0.851 (14)	C3—H3A	0.95
O3—N1	1.2267 (14)	C4—C5	1.3800 (17)
O4—N1	1.2271 (14)	C5—C6	1.3874 (18)
N1—C4	1.4718 (16)	C5—H5A	0.95
C1—C6	1.3950 (18)	C6—H6A	0.95

C7—O2—H2	108.7 (12)	C4—C5—C6	117.93 (11)
O3—N1—O4	124.05 (11)	C4—C5—H5A	121.0
O3—N1—C4	118.02 (10)	C6—C5—H5A	121.0
O4—N1—C4	117.93 (10)	C5—C6—C1	120.94 (11)
C6—C1—C2	119.61 (11)	C5—C6—H6A	119.5
C6—C1—C7	117.45 (11)	C1—C6—H6A	119.5
C2—C1—C7	122.91 (11)	O1—C7—O2	124.95 (12)
C3—C2—C1	120.02 (11)	O1—C7—C1	122.01 (12)
C3—C2—C8	117.65 (11)	O2—C7—C1	113.00 (11)
C1—C2—C8	122.18 (11)	F2—C8—F3	107.01 (11)
C2—C3—C4	118.48 (11)	F2—C8—F1	106.28 (11)
C2—C3—H3A	120.8	F3—C8—F1	106.84 (11)
C4—C3—H3A	120.8	F2—C8—C2	111.84 (11)
C5—C4—C3	122.98 (11)	F3—C8—C2	111.48 (11)
C5—C4—N1	119.23 (11)	F1—C8—C2	113.01 (11)
C3—C4—N1	117.79 (10)

C6—C1—C2—C3	1.57 (18)	C4—C5—C6—C1	0.26 (19)
C7—C1—C2—C3	−176.30 (12)	C2—C1—C6—C5	−1.91 (19)
C6—C1—C2—C8	−173.81 (12)	C7—C1—C6—C5	176.08 (12)
C7—C1—C2—C8	8.32 (19)	C6—C1—C7—O1	−130.98 (14)
C1—C2—C3—C4	0.39 (18)	C2—C1—C7—O1	46.94 (19)
C8—C2—C3—C4	175.97 (11)	C6—C1—C7—O2	46.69 (16)
C2—C3—C4—C5	−2.13 (19)	C2—C1—C7—O2	−135.40 (13)
C2—C3—C4—N1	178.49 (11)	C3—C2—C8—F2	−15.31 (17)
O3—N1—C4—C5	−178.53 (12)	C1—C2—C8—F2	160.17 (12)
O4—N1—C4—C5	1.73 (17)	C3—C2—C8—F3	−135.07 (12)
O3—N1—C4—C3	0.87 (17)	C1—C2—C8—F3	40.41 (17)
O4—N1—C4—C3	−178.87 (11)	C3—C2—C8—F1	104.58 (14)
C3—C4—C5—C6	1.80 (19)	C1—C2—C8—F1	−79.94 (15)
N1—C4—C5—C6	−178.82 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.85 (1)	1.86 (2)	2.7042 (14)	175 (2)
C3—H3A···F3ⁱⁱ	0.95	2.47	3.3942 (15)	164

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

4-Nitro-3-(trifluoromethyl)benzoic acid (II) top

Crystal data top

C₈H₄F₃NO₄	F(000) = 472
M_r = 235.12	D_x = 1.792 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.8986 (8) Å	Cell parameters from 9889 reflections
b = 17.240 (2) Å	θ = 2.4–30.5°
c = 7.6912 (9) Å	µ = 0.18 mm⁻¹
β = 107.685 (2)°	T = 125 K
V = 871.50 (18) Å³	Plate, colourless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2665 independent reflections
Radiation source: fine-focus sealed tube	2116 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.071
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.5°, θ_min = 2.4°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008a)	k = 0→24
T_min = 0.89, T_max = 0.98	l = 0→10
4385 measured reflections

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.0909P)² + 0.092P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2873 reflections	Δρ_max = 0.50 e Å⁻³
150 parameters	Δρ_min = −0.35 e Å⁻³

Special details top

Refinement. Refined as a 3-component twin. BASF 0.0961 (3) 0.0326 (2)

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

	x	y	z	U_iso*/U_eq
F1	0.86853 (17)	0.33150 (8)	0.38868 (15)	0.0394 (3)
F2	0.78710 (18)	0.23188 (6)	0.51840 (16)	0.0356 (3)
F3	0.97458 (14)	0.32129 (6)	0.68002 (13)	0.0258 (3)
O1	0.03937 (17)	0.49961 (7)	0.22770 (15)	0.0228 (3)
O2	0.22198 (18)	0.44236 (8)	0.06814 (16)	0.0242 (3)
H2	0.136 (3)	0.4651 (13)	−0.015 (3)	0.029*
O3	0.7408 (2)	0.25918 (8)	0.88052 (18)	0.0303 (3)
O4	0.7540 (2)	0.37201 (10)	1.00889 (17)	0.0386 (4)
N1	0.7034 (2)	0.32815 (9)	0.87729 (19)	0.0220 (3)
C1	0.3254 (2)	0.42454 (9)	0.3879 (2)	0.0152 (3)
C2	0.4976 (2)	0.38357 (9)	0.3829 (2)	0.0158 (3)
H2A	0.527015	0.377515	0.27074	0.019*
C3	0.6270 (2)	0.35142 (9)	0.5426 (2)	0.0157 (3)
C4	0.5782 (2)	0.36199 (9)	0.7032 (2)	0.0164 (3)
C5	0.4107 (2)	0.40416 (10)	0.7112 (2)	0.0210 (3)
H5A	0.384027	0.411841	0.824123	0.025*
C6	0.2823 (2)	0.43502 (10)	0.5510 (2)	0.0192 (3)
H6A	0.16486	0.463335	0.552985	0.023*
C7	0.1847 (2)	0.45815 (9)	0.2175 (2)	0.0168 (3)
C8	0.8138 (2)	0.30861 (10)	0.5324 (2)	0.0216 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0313 (6)	0.0661 (9)	0.0253 (6)	0.0241 (6)	0.0153 (5)	0.0160 (5)
F2	0.0352 (6)	0.0242 (6)	0.0408 (7)	0.0118 (4)	0.0016 (5)	−0.0074 (5)
F3	0.0144 (4)	0.0356 (6)	0.0241 (5)	0.0043 (4)	0.0008 (4)	0.0032 (4)
O1	0.0203 (6)	0.0266 (6)	0.0190 (6)	0.0099 (5)	0.0023 (4)	−0.0002 (4)
O2	0.0243 (6)	0.0307 (7)	0.0155 (5)	0.0114 (5)	0.0027 (5)	0.0023 (5)
O3	0.0330 (7)	0.0253 (7)	0.0316 (7)	0.0080 (5)	0.0083 (6)	0.0120 (5)
O4	0.0482 (9)	0.0425 (9)	0.0169 (6)	0.0057 (7)	−0.0024 (6)	−0.0009 (6)
N1	0.0189 (6)	0.0279 (8)	0.0186 (7)	0.0042 (5)	0.0050 (5)	0.0076 (5)
C1	0.0138 (6)	0.0145 (7)	0.0156 (7)	0.0004 (5)	0.0018 (5)	0.0012 (5)
C2	0.0151 (6)	0.0165 (7)	0.0151 (7)	0.0011 (5)	0.0034 (5)	0.0005 (5)
C3	0.0141 (6)	0.0148 (7)	0.0167 (7)	0.0011 (5)	0.0022 (5)	0.0005 (5)
C4	0.0160 (7)	0.0154 (7)	0.0155 (7)	0.0002 (5)	0.0016 (5)	0.0029 (5)
C5	0.0208 (7)	0.0262 (9)	0.0173 (7)	0.0035 (6)	0.0076 (6)	0.0028 (6)
C6	0.0154 (7)	0.0217 (8)	0.0198 (7)	0.0037 (6)	0.0044 (6)	0.0012 (6)
C7	0.0168 (6)	0.0159 (7)	0.0161 (7)	0.0018 (5)	0.0028 (5)	−0.0002 (5)
C8	0.0197 (7)	0.0255 (8)	0.0180 (7)	0.0073 (6)	0.0035 (6)	0.0033 (6)

Geometric parameters (Å, º) top

F1—C8	1.332 (2)	C1—C2	1.393 (2)
F2—C8	1.335 (2)	C1—C7	1.491 (2)
F3—C8	1.3424 (18)	C2—C3	1.395 (2)
O1—C7	1.2528 (18)	C2—H2A	0.95
O2—C7	1.281 (2)	C3—C4	1.387 (2)
O2—H2	0.826 (16)	C3—C8	1.508 (2)
O3—N1	1.2154 (19)	C4—C5	1.383 (2)
O4—N1	1.226 (2)	C5—C6	1.387 (2)
N1—C4	1.4751 (19)	C5—H5A	0.95
C1—C6	1.386 (2)	C6—H6A	0.95

C7—O2—H2	107.5 (16)	C4—C5—C6	118.62 (15)
O3—N1—O4	125.51 (15)	C4—C5—H5A	120.7
O3—N1—C4	117.88 (14)	C6—C5—H5A	120.7
O4—N1—C4	116.54 (15)	C1—C6—C5	119.98 (15)
C6—C1—C2	120.69 (13)	C1—C6—H6A	120.0
C6—C1—C7	118.92 (14)	C5—C6—H6A	120.0
C2—C1—C7	120.39 (14)	O1—C7—O2	124.04 (14)
C1—C2—C3	120.00 (14)	O1—C7—C1	119.12 (14)
C1—C2—H2A	120.0	O2—C7—C1	116.84 (13)
C3—C2—H2A	120.0	F1—C8—F2	107.05 (14)
C4—C3—C2	117.95 (14)	F1—C8—F3	106.48 (14)
C4—C3—C8	123.56 (13)	F2—C8—F3	106.73 (13)
C2—C3—C8	118.48 (14)	F1—C8—C3	111.13 (13)
C5—C4—C3	122.73 (14)	F2—C8—C3	112.97 (14)
C5—C4—N1	115.73 (14)	F3—C8—C3	112.10 (14)
C3—C4—N1	121.53 (14)

C6—C1—C2—C3	1.1 (2)	C2—C1—C6—C5	−0.4 (2)
C7—C1—C2—C3	−179.15 (14)	C7—C1—C6—C5	179.87 (15)
C1—C2—C3—C4	−0.2 (2)	C4—C5—C6—C1	−1.2 (2)
C1—C2—C3—C8	−179.01 (14)	C6—C1—C7—O1	5.0 (2)
C2—C3—C4—C5	−1.5 (2)	C2—C1—C7—O1	−174.71 (15)
C8—C3—C4—C5	177.26 (15)	C6—C1—C7—O2	−175.09 (15)
C2—C3—C4—N1	178.27 (14)	C2—C1—C7—O2	5.2 (2)
C8—C3—C4—N1	−3.0 (2)	C4—C3—C8—F1	−155.52 (15)
O3—N1—C4—C5	127.62 (17)	C2—C3—C8—F1	23.2 (2)
O4—N1—C4—C5	−49.6 (2)	C4—C3—C8—F2	84.14 (19)
O3—N1—C4—C3	−52.1 (2)	C2—C3—C8—F2	−97.15 (17)
O4—N1—C4—C3	130.66 (17)	C4—C3—C8—F3	−36.5 (2)
C3—C4—C5—C6	2.2 (2)	C2—C3—C8—F3	142.23 (14)
N1—C4—C5—C6	−177.56 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.83 (2)	1.82 (2)	2.6337 (16)	168 (2)
C5—H5A···O2ⁱⁱ	0.95	2.51	3.440 (2)	165

Symmetry codes: (i) −x, −y+1, −z; (ii) x, y, z+1.

Funding information

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (Grants Nos. 0521237 and 0911324 to JMT). We acknowledge the Salmon Fund of Vassar College for funding publication expenses.

References

Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science Google Scholar
Bruker (2013). SAINT, SADABS and APEX2. Bruxer AXS Inc., Madison, Wisconsin, USA. Google Scholar
Caldwell, W. T. & Sayin, A. N. (1951). J. Am. Chem. Soc. 73, 5125–5127. CrossRef CAS Google Scholar
Cheung, M., Demartino, M. P., Eidam, H. S., Guan, H. A., Qin, D., Wu, C., Gong, Z., Yang, H., Yu, H. & Zhang, Z. (2017). WO Patent 2016037578 A1. Google Scholar
Di Raddo, P. (1993). J. Chem. Educ. 70, 1034. CrossRef Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Kompella, A., Gampa, V. K., Ganganamoni, S., Sirigireddy, B. R., Adibhatla, K. S. B. R. & Nannapaneni, V. C. (2017). US Patent 20170114057 A1. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nishio, Y., Kubota, Y., Yamamoto, M., Nishimura, Y., Masuda, T., Tsutsui, H., Okimura, K., Udagawa, S., Kaino, M., Meguro, H. & Sekiya, Y. (2017). WO Patent 2017038873 A1. Google Scholar
Saha, S., Rajput, L., Joseph, S., Mishra, M. K., Ganguly, S. & Desiraju, G. R. (2015). CrystEngComm, 17, 1273–1290. Web of Science CrossRef CAS Google Scholar
Selvam, C., Lemasson, I. A., Brabet, I., Oueslati, N., Karaman, B., Cabaye, A., Tora, A. S., Commare, B., Courtiol, T., Cesarini, S., McCort-Tranchepain, I., Rigault, D., Mony, L., Bessiron, T., McLean, H., Leroux, F. R., Colobert, F., Daniel, H., Goupil-Lamy, A., Bertrand, H. O., Goudet, C., Pin, J. P. & Acher, F. C. (2018). J. Med. Chem. 61, 1969–1989. CrossRef CAS Google Scholar
Sheldrick, G. M. (2003). CELL_NOW, University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008a). TWINABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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

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Volume 75| Part 4| April 2019| Pages 524-528

https://doi.org/10.1107/S2056989019003979

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystallographic and spectroscopic character­ization of 4-nitro-2-(tri­fluoro­meth­yl)benzoic acid and 4-nitro-3-(tri­fluoro­meth­yl)benzoic acid

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

7. Analytical data

Supporting information

Funding information

References

research communications

Crystallographic and spectroscopic characterization of 4-nitro-2-(trifluoromethyl)benzoic acid and 4-nitro-3-(trifluoromethyl)benzoic acid

3. Supramolecular features