4-Meth­oxy-2-nitro-4′-(trifluoro­meth­yl)biphen­yl

Abstract

The title compound, C₁₄H₁₀F₃NO₃, was prepared by a palladium-catalysed Suzuki–Miyaura coupling reaction. The dihedral angle between the nitro group and its parent benzene ring is 66.85 (19)° while the dihedral angle between the two benzene rings is 49.98 (9)°. The CF₃ group is disordered over two sets of sites with occupancies of 0.457 (8) and 0.543 (8).

Related literature

For general background to the synthesis and properties of the title compound, see: Suzuki (1999 ▶); Razler et al. (2009 ▶). For the biological activity of biphenyl derivatives, see: Kimpe et al. (1996 ▶).

Experimental

Crystal data

• C₁₄H₁₀F₃NO₃

• M _r = 297.23

• Monoclinic,

• a = 8.1956 (13) Å

• b = 20.777 (3) Å

• c = 7.9715 (12) Å

• β = 104.240 (2)°

• V = 1315.7 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.13 mm⁻¹

• T = 293 K

• 0.26 × 0.24 × 0.20 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.966, T _max = 0.974

• 10512 measured reflections

• 3235 independent reflections

• 1910 reflections with I > 2σ(I)

• R _int = 0.029

Refinement

• R[F ² > 2σ(F ²)] = 0.050

• wR(F ²) = 0.161

• S = 1.05

• 3235 reflections

• 243 parameters

• 36 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811039092/ff2027Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811039092/ff2027Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

To a solution of 4-bromo-trifluoromethylphenyl (5 mmol) and 4-methoxy-2-nitro-phenylboronic acid (6 mmol) in 20 ml water and 20 ml methanol was added Pd(OAc)₂ (5 mmol) and K₂CO₃ (10 mmol). After stirring the reaction mixture for 12 h at room temperature, the aqueous phases were extracted with 100 ml ethyl acetate. The organic extracts were washed with 200 ml saturated aqueous sodium chloride, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting crude material was purified via silica gel chromatography (5% ethyl acetate/hexane) to afford a translucent solid in a yield of 80%. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from methanol at room temperature in a total yield of 32%. Analysis found: C 56.6, H 3.3, N 4.6%; C₁₄H₁₀F₃NO₃ requires: C 56.6, H 3.4, N 4.7%. ₁H NMR (400 MHz, CDCl₃) 7.66 (d, J = 8.1 Hz, 2H), 7.45 (d, J = 2.6 Hz, 1H), 7.40 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.5 Hz, 1H), 7.19 (dd, J = 8.6, 2.6 Hz, 1H), 3.92 (s, 3H).

Refinement

All H-atoms were positioned geometrically and included in the refinement in the riding-model approximation, with U_iso(H)= 1.5Ueq(methyl C) and 1.2Ueq(aromatic C). The –CF₃ group is disordered over two sites with occupancies of 0.457 (8) and 0.543 (8). For this fragment, some anisotropic displacement ellipsoids were rather elongated which led us to use the ISOR restraints (Sheldrick, 2008).

Figures

Fig. 1.

The structure of (I) with 50% probability displacement ellipsoids for non-hydrogen atoms showing the disordered –CF3 group.

Crystal data

C14H10F3NO3	F(000) = 608
Mr = 297.23	Dx = 1.501 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1880 reflections
a = 8.1956 (13) Å	θ = 2.8–22.6°
b = 20.777 (3) Å	µ = 0.13 mm−1
c = 7.9715 (12) Å	T = 293 K
β = 104.240 (2)°	Block, colorless
V = 1315.7 (3) Å3	0.26 × 0.24 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	3235 independent reflections
Radiation source: fine-focus sealed tube	1910 reflections with I > 2σ(I)
graphite	Rint = 0.029
phi and ω scans	θmax = 28.3°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.966, Tmax = 0.974	k = −27→27
10512 measured reflections	l = −10→10

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.161	w = 1/[σ2(Fo2) + (0.0741P)2 + 0.1504P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3235 reflections	Δρmax = 0.30 e Å−3
243 parameters	Δρmin = −0.21 e Å−3
36 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.026 (4)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1A	0.6447 (4)	0.19880 (14)	0.4301 (4)	0.0705 (7)	0.46
F1A	0.6131 (8)	0.1395 (3)	0.3972 (18)	0.147 (3)	0.46
F2A	0.7487 (9)	0.2001 (4)	0.5832 (6)	0.108 (2)	0.46
F3A	0.7514 (8)	0.2162 (4)	0.3299 (10)	0.1111 (16)	0.46
C1B	0.6447 (4)	0.19880 (14)	0.4301 (4)	0.0705 (7)	0.54
F1B	0.6331 (8)	0.1469 (3)	0.5270 (8)	0.1152 (18)	0.54
F2B	0.7864 (6)	0.2248 (3)	0.4985 (14)	0.142 (2)	0.54
F3B	0.6443 (9)	0.1723 (3)	0.2844 (5)	0.1143 (16)	0.54
O3	−0.3255 (2)	0.48543 (8)	0.4265 (2)	0.0667 (5)
N1	0.0999 (2)	0.42470 (11)	0.1294 (2)	0.0604 (5)
C2	0.4994 (3)	0.24308 (11)	0.4159 (3)	0.0549 (6)
C3	0.5169 (3)	0.30787 (12)	0.3869 (3)	0.0581 (6)
C4	0.3843 (3)	0.34936 (11)	0.3798 (3)	0.0551 (6)
C5	0.2308 (3)	0.32692 (10)	0.4005 (3)	0.0496 (5)
C6	0.2145 (3)	0.26131 (11)	0.4274 (3)	0.0573 (6)
C7	0.3473 (3)	0.21981 (12)	0.4348 (3)	0.0606 (6)
C8	0.0882 (3)	0.37089 (10)	0.4025 (3)	0.0485 (5)
C9	0.0257 (3)	0.41719 (10)	0.2790 (3)	0.0484 (5)
C10	−0.1091 (3)	0.45702 (10)	0.2791 (3)	0.0504 (5)
C11	−0.1881 (3)	0.45081 (10)	0.4134 (3)	0.0512 (5)
C12	−0.1259 (3)	0.40693 (11)	0.5441 (3)	0.0574 (6)
H12	−0.1751	0.4039	0.6372	0.069*
C13	0.0072 (3)	0.36797 (11)	0.5379 (3)	0.0568 (6)
C14	−0.4039 (3)	0.52531 (14)	0.2844 (4)	0.0754 (8)
H14A	−0.3272	0.5585	0.2700	0.113*
H14B	−0.5032	0.5445	0.3064	0.113*
H14C	−0.4343	0.4998	0.1810	0.113*
H10	−0.146 (3)	0.4878 (10)	0.188 (3)	0.053 (6)*
H4	0.401 (3)	0.3937 (11)	0.364 (3)	0.064 (7)*
H11	0.044 (3)	0.3381 (11)	0.630 (3)	0.063 (6)*
H6	0.112 (3)	0.2454 (11)	0.442 (3)	0.062 (6)*
H7	0.332 (3)	0.1735 (12)	0.454 (3)	0.067 (7)*
H3	0.622 (3)	0.3236 (11)	0.371 (3)	0.068 (7)*
O2	0.1707 (3)	0.47594 (11)	0.1180 (3)	0.0972 (7)
O1	0.0856 (3)	0.38237 (10)	0.0266 (3)	0.1025 (8)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1A	0.0697 (18)	0.0762 (18)	0.0648 (17)	0.0077 (14)	0.0150 (13)	−0.0032 (14)
F1A	0.114 (4)	0.079 (3)	0.239 (7)	0.007 (3)	0.025 (6)	−0.054 (5)
F2A	0.099 (4)	0.151 (6)	0.063 (2)	0.062 (4)	−0.001 (2)	0.004 (3)
F3A	0.089 (3)	0.141 (4)	0.123 (4)	0.043 (3)	0.061 (3)	0.041 (3)
C1B	0.0697 (18)	0.0762 (18)	0.0648 (17)	0.0077 (14)	0.0150 (13)	−0.0032 (14)
F1B	0.126 (4)	0.116 (4)	0.115 (3)	0.066 (3)	0.053 (3)	0.055 (3)
F2B	0.065 (2)	0.122 (4)	0.221 (6)	0.017 (2)	0.002 (4)	−0.038 (4)
F3B	0.151 (4)	0.128 (3)	0.070 (2)	0.067 (3)	0.039 (2)	−0.007 (2)
O3	0.0589 (10)	0.0774 (11)	0.0701 (11)	0.0099 (8)	0.0280 (8)	0.0027 (8)
N1	0.0601 (12)	0.0727 (13)	0.0524 (11)	0.0114 (10)	0.0215 (9)	0.0146 (10)
C2	0.0553 (13)	0.0601 (13)	0.0466 (12)	0.0065 (11)	0.0076 (10)	−0.0014 (9)
C3	0.0517 (13)	0.0662 (15)	0.0568 (13)	−0.0055 (11)	0.0139 (10)	−0.0024 (11)
C4	0.0562 (14)	0.0512 (13)	0.0586 (13)	−0.0068 (11)	0.0152 (10)	0.0017 (10)
C5	0.0518 (12)	0.0518 (12)	0.0436 (11)	−0.0029 (10)	0.0085 (9)	0.0027 (9)
C6	0.0535 (14)	0.0536 (13)	0.0655 (14)	−0.0051 (11)	0.0161 (11)	0.0067 (10)
C7	0.0651 (15)	0.0524 (13)	0.0637 (14)	0.0005 (12)	0.0148 (11)	0.0058 (11)
C8	0.0477 (12)	0.0475 (11)	0.0501 (12)	−0.0066 (9)	0.0115 (9)	0.0023 (9)
C9	0.0518 (12)	0.0519 (11)	0.0438 (11)	−0.0031 (9)	0.0166 (9)	0.0019 (9)
C10	0.0531 (12)	0.0499 (11)	0.0501 (12)	0.0002 (10)	0.0161 (10)	0.0056 (10)
C11	0.0489 (12)	0.0529 (12)	0.0545 (12)	−0.0062 (10)	0.0176 (10)	−0.0032 (10)
C12	0.0590 (14)	0.0657 (14)	0.0529 (12)	−0.0066 (11)	0.0243 (10)	0.0026 (10)
C13	0.0611 (14)	0.0604 (13)	0.0492 (12)	−0.0040 (11)	0.0144 (10)	0.0104 (10)
C14	0.0611 (16)	0.0862 (18)	0.0803 (18)	0.0158 (14)	0.0201 (13)	0.0066 (14)
O2	0.1010 (15)	0.1191 (17)	0.0805 (14)	−0.0256 (13)	0.0393 (12)	0.0224 (12)
O1	0.149 (2)	0.0977 (15)	0.0789 (13)	0.0180 (14)	0.0628 (14)	−0.0116 (11)

Geometric parameters (Å, °)

C1A—F1A	1.273 (6)	C5—C8	1.487 (3)
C1A—F2A	1.306 (6)	C6—C7	1.378 (3)
C1A—F3A	1.370 (5)	C6—H6	0.93 (2)
C1A—C2	1.487 (3)	C7—H7	0.99 (2)
O3—C11	1.361 (3)	C8—C9	1.381 (3)
O3—C14	1.423 (3)	C8—C13	1.401 (3)
N1—O1	1.188 (3)	C9—C10	1.381 (3)
N1—O2	1.226 (3)	C10—C11	1.387 (3)
N1—C9	1.474 (2)	C10—H10	0.96 (2)
C2—C3	1.379 (3)	C11—C12	1.384 (3)
C2—C7	1.380 (3)	C12—C13	1.369 (3)
C3—C4	1.377 (3)	C12—H12	0.9300
C3—H3	0.96 (2)	C13—H11	0.95 (2)
C4—C5	1.389 (3)	C14—H14A	0.9600
C4—H4	0.94 (2)	C14—H14B	0.9600
C5—C6	1.391 (3)	C14—H14C	0.9600
F1A—C1A—F2A	105.4 (6)	C6—C7—H7	119.2 (14)
F1A—C1A—F3A	105.2 (5)	C2—C7—H7	120.7 (14)
F2A—C1A—F3A	100.1 (5)	C9—C8—C13	114.61 (19)
F1A—C1A—C2	117.7 (4)	C9—C8—C5	125.07 (17)
F2A—C1A—C2	112.6 (3)	C13—C8—C5	120.31 (19)
F3A—C1A—C2	114.0 (3)	C10—C9—C8	124.99 (18)
C11—O3—C14	117.82 (17)	C10—C9—N1	115.23 (18)
O1—N1—O2	124.0 (2)	C8—C9—N1	119.73 (18)
O1—N1—C9	119.3 (2)	C9—C10—C11	118.1 (2)
O2—N1—C9	116.6 (2)	C9—C10—H10	120.4 (12)
C3—C2—C7	119.6 (2)	C11—C10—H10	121.5 (12)
C3—C2—C1A	120.2 (2)	O3—C11—C12	116.66 (18)
C7—C2—C1A	120.2 (2)	O3—C11—C10	124.2 (2)
C4—C3—C2	120.3 (2)	C12—C11—C10	119.1 (2)
C4—C3—H3	120.5 (14)	C13—C12—C11	120.76 (19)
C2—C3—H3	119.2 (14)	C13—C12—H12	119.6
C3—C4—C5	120.9 (2)	C11—C12—H12	119.6
C3—C4—H4	118.5 (15)	C12—C13—C8	122.4 (2)
C5—C4—H4	120.6 (15)	C12—C13—H11	117.6 (14)
C4—C5—C6	118.1 (2)	C8—C13—H11	120.1 (14)
C4—C5—C8	122.17 (19)	O3—C14—H14A	109.5
C6—C5—C8	119.66 (19)	O3—C14—H14B	109.5
C7—C6—C5	121.0 (2)	H14A—C14—H14B	109.5
C7—C6—H6	119.8 (14)	O3—C14—H14C	109.5
C5—C6—H6	119.2 (14)	H14A—C14—H14C	109.5
C6—C7—C2	120.1 (2)	H14B—C14—H14C	109.5
F1A—C1A—C2—C3	−156.3 (8)	C13—C8—C9—C10	−2.3 (3)
F2A—C1A—C2—C3	80.8 (6)	C5—C8—C9—C10	178.5 (2)
F3A—C1A—C2—C3	−32.4 (6)	C13—C8—C9—N1	−179.6 (2)
F1A—C1A—C2—C7	24.9 (8)	C5—C8—C9—N1	1.2 (3)
F2A—C1A—C2—C7	−98.0 (6)	O1—N1—C9—C10	−111.7 (2)
F3A—C1A—C2—C7	148.7 (5)	O2—N1—C9—C10	66.8 (3)
C7—C2—C3—C4	1.1 (3)	O1—N1—C9—C8	65.8 (3)
C1A—C2—C3—C4	−177.7 (2)	O2—N1—C9—C8	−115.6 (2)
C2—C3—C4—C5	−0.4 (3)	C8—C9—C10—C11	0.5 (3)
C3—C4—C5—C6	−0.4 (3)	N1—C9—C10—C11	177.87 (19)
C3—C4—C5—C8	176.8 (2)	C14—O3—C11—C12	−172.8 (2)
C4—C5—C6—C7	0.5 (3)	C14—O3—C11—C10	7.2 (3)
C8—C5—C6—C7	−176.7 (2)	C9—C10—C11—O3	−177.8 (2)
C5—C6—C7—C2	0.2 (4)	C9—C10—C11—C12	2.2 (3)
C3—C2—C7—C6	−1.0 (3)	O3—C11—C12—C13	177.1 (2)
C1A—C2—C7—C6	177.8 (2)	C10—C11—C12—C13	−2.9 (3)
C4—C5—C8—C9	50.9 (3)	C11—C12—C13—C8	0.9 (4)
C6—C5—C8—C9	−131.9 (2)	C9—C8—C13—C12	1.6 (3)
C4—C5—C8—C13	−128.2 (2)	C5—C8—C13—C12	−179.2 (2)
C6—C5—C8—C13	48.9 (3)