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

Hou, Y.-J.; Li, X.-M.; Chu, W.-Y.; Sun, Z.-Z.

doi:10.1107/S1600536811039092

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2915

doi:10.1107/S1600536811039092

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

Yan-Jun Hou,^a Xin-Min Li,^a Wen-Yi Chu ^a and Zhi-Zhong Sun ^a ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hljusunzhizhong@163.com

(Received 16 September 2011; accepted 23 September 2011; online 12 October 2011)

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, P 2₁ /c
a = 8.1956 (13) Å
b = 20.777 (3) Å
c = 7.9715 (12) Å
β = 104.240 (2)°
V = 1315.7 (3) Å³
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[F² > 2σ(F²)] = 0.050
wR(F²) = 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811039092/ff2027sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811039092/ff2027Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811039092/ff2027Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811039092/ff2027Isup4.cml

checkCIF report

Related literature top

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 top

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).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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).

Figures top

Fig. 1. The structure of (I) with 50% probability displacement ellipsoids for non-hydrogen atoms showing the disordered –CF₃ group.

4-Methoxy-2-nitro-4'-(trifluoromethyl)biphenyl top

Crystal data top

C₁₄H₁₀F₃NO₃	F(000) = 608
M_r = 297.23	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0741P)² + 0.1504P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3235 reflections	Δρ_max = 0.30 e Å⁻³
243 parameters	Δρ_min = −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)

Crystal data top

C₁₄H₁₀F₃NO₃	V = 1315.7 (3) Å³
M_r = 297.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1956 (13) Å	µ = 0.13 mm⁻¹
b = 20.777 (3) Å	T = 293 K
c = 7.9715 (12) Å	0.26 × 0.24 × 0.20 mm
β = 104.240 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3235 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1910 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.974	R_int = 0.029
10512 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	36 restraints
wR(F²) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.30 e Å⁻³
3235 reflections	Δρ_min = −0.21 e Å⁻³
243 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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, º) top

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)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀F₃NO₃
M_r	297.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.1956 (13), 20.777 (3), 7.9715 (12)
β (°)	104.240 (2)
V (Å³)	1315.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	10512, 3235, 1910
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.161, 1.05
No. of reflections	3235
No. of parameters	243
No. of restraints	36
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.21

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

We thank the National Natural Science Foundation of China (No. 20872030) and Heilongjiang University, China, for supporting this study.

References

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