1,1,1,3,3,3-Hexa­fluoro-2-(4-nitro­phenyl)-N-phenyl­iso­propyl­amine

Pavkovic, S.F.; Nelson, D.W.; Owens, J.R.

doi:10.1107/S1600536801014763

1,1,1,3,3,3-Hexafluoro-2-(4-nitrophenyl)-N-phenylisopropylamine

S. F. Pavkovic, D. W. Nelson and J. R. Owens

There is no interaction between the amine H and any F atom in the title compound, C₁₅H₁₀F₆N₂O₂. Rather the amine H atom is hydrogen bonded to one of the nitro group O atoms on a neighboring molecule. This hydrogen bonding operates in the direction of the minor axis and links molecules into infinite chains.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014763/om6049sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014763/om6049Isup2.hkl Contains datablock I

CCDC reference: 175359

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.059
wR factor = 0.173
Data-to-parameter ratio = 25.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



DENSM_01  Alert B _exptl_crystal_density_method is given but no value of
          _exptl_crystal_density_meas is reported.


 Alert Level C:



PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C4   -C5      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C4   -C9      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C5   -C6      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C6   -C7      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C7   -C8      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C8   -C9      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C10  -C11     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C10  -C15     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C11  -C12     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C12  -C13     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C13  -C14     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C14  -C15     1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(16), Rep      120.00 ....    Missing s.u.
                     C5   -C4   -C9      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(16), Rep      120.00 ....    Missing s.u.
                     C6   -C5   -C4      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(17), Rep      120.00 ....    Missing s.u.
                     C7   -C6   -C5      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  119.99(16), Rep      120.00 ....    Missing s.u.
                     C8   -C7   -C6      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(17), Rep      120.00 ....    Missing s.u.
                     C7   -C8   -C9      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  119.99(17), Rep      120.00 ....    Missing s.u.
                     C8   -C9   -C4      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(15), Rep      120.00 ....    Missing s.u.
                     C11  -C10  -C15     1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(17), Rep      120.00 ....    Missing s.u.
                     C12  -C11  -C10     1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(18), Rep      120.00 ....    Missing s.u.
                     C11  -C12  -C13     1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(16), Rep      120.00 ....    Missing s.u.
                     C14  -C13  -C12     1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(17), Rep      120.00 ....    Missing s.u.
                     C15  -C14  -C13     1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc  120.00(17), Rep      120.00 ....    Missing s.u.
                     C14  -C15  -C10     1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C9  -C4  -C5  -C6     1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C4  -C5  -C6  -C7     1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(4), Rep        0.00 ....    Missing s.u.
                     C5  -C6  -C7  -C8     1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(4), Rep        0.00 ....    Missing s.u.
                     C6  -C7  -C8  -C9     1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C7  -C8  -C9  -C4     1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C5  -C4  -C9  -C8     1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C15 -C10 -C11 -C12    1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C10 -C11 -C12 -C13    1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(4), Rep        0.00 ....    Missing s.u.
                     C11 -C12 -C13 -C14    1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(4), Rep        0.00 ....    Missing s.u.
                     C12 -C13 -C14 -C15    1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C13 -C14 -C15 -C10    1.555   1.555   1.555   1.555

PLAT_743  Alert C Torsion Calc      0.0(3), Rep        0.00 ....    Missing s.u.
                     C11 -C10 -C15 -C14    1.555   1.555   1.555   1.555


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 36 Alert Level C = Please check

Comment top

(Trifluoromethyl)trimethylsilane reacts with nitrones to afford α-(trifluoromethyl)hydroxylamines, protected as O-trimethylsilyl ethers. Adducts with strong electron-withdrawing groups on the α-aryl ring undergo an elimination/addition sequence to produce α,α-bis(trifluoromethyl)amines. The structure of compound, (I), produced from the p-nitrophenyl adduct is reported here.

Experimental top

The preparation of (I) has been reported (Nelson et al., 2001). Crystals suitable for diffraction analysis were obtained from hexane.

Computing details top

Data collection: XSTAL (Brown, 1985), a modification of Picker FACS-I software (Picker, 1967); cell refinement: CELL (Brown, 1985); data reduction: MINCON (Brown, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997).

Figures top

Fig. 1. Displacement ellipsoid plot of the title compound with ellipsoids at the 50% probability level and H atoms omitted for clarity.

1,1,1,3,3,3-Hexafluoro-2-(4-nitrophenyl)-N-phenylisopropylamine top

Crystal data top

C₁₅H₁₀F₆N₂O₂	D_x = 1.619 Mg m⁻³ D_m = more dense than CCl₄ Mg m⁻³ D_m measured by flotation
M_r = 364.25	Melting point = 180–182 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
a = 16.903 (3) Å	Cell parameters from 13 reflections
b = 10.182 (2) Å	θ = 10–12.5°
c = 17.971 (3) Å	µ = 0.16 mm⁻¹
β = 104.90 (1)°	T = 293 K
V = 2989.1 (9) Å³	Cut fragment, pale yellow
Z = 8	0.40 × 0.35 × 0.25 mm
F(000) = 1472

Data collection top

Picker four-circle diffractometer	R_int = 0.056
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.4°
None monochromator	h = −22→18
θ/2θ scans	k = −7→13
7110 measured reflections	l = −23→23
3603 independent reflections	4 standard reflections every 150 reflections
1373 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.059	H-atom parameters constrained
wR(F²) = 0.173	w = [exp{1.30(sinθ/λ)²}]/[σ²(F_o²) + (0.0559P)²] where P = 0.33F_o² + 0.67F_c²
S = 0.98	(Δ/σ)_max = 0.010
3603 reflections	Δρ_max = 0.51 e Å⁻³
143 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (3)

Crystal data top

C₁₅H₁₀F₆N₂O₂	V = 2989.1 (9) Å³
M_r = 364.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 16.903 (3) Å	µ = 0.16 mm⁻¹
b = 10.182 (2) Å	T = 293 K
c = 17.971 (3) Å	0.40 × 0.35 × 0.25 mm
β = 104.90 (1)°

Data collection top

Picker four-circle diffractometer	R_int = 0.056
7110 measured reflections	4 standard reflections every 150 reflections
3603 independent reflections	intensity decay: <1%
1373 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 0.98	Δρ_max = 0.51 e Å⁻³
3603 reflections	Δρ_min = −0.26 e Å⁻³
143 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
C1	0.3495 (2)	0.2893 (3)	0.36500 (19)	0.0458 (9)
C2	0.2547 (3)	0.2785 (4)	0.3498 (2)	0.0611 (10)
C3	0.3877 (3)	0.2369 (4)	0.4466 (2)	0.0589 (10)
C4	0.37909 (12)	0.43107 (15)	0.36294 (12)	0.0394 (8)*
C5	0.45588 (11)	0.44937 (17)	0.34983 (13)	0.0459 (8)*
H5	0.4870	0.3771	0.3432	0.055*
C6	0.48610 (10)	0.5756 (2)	0.34666 (13)	0.0527 (9)*
H6	0.5375	0.5879	0.3379	0.063*
C7	0.43954 (12)	0.68359 (16)	0.35660 (14)	0.0506 (9)*
C8	0.36275 (12)	0.66529 (17)	0.36970 (13)	0.0500 (9)*
H8	0.3316	0.7375	0.3763	0.060*
C9	0.33252 (10)	0.53903 (19)	0.37287 (13)	0.0472 (9)*
H9	0.2811	0.5268	0.3816	0.057*
C10	0.36723 (13)	0.2257 (2)	0.23300 (8)	0.0407 (8)*
C11	0.39275 (14)	0.12231 (17)	0.19429 (11)	0.0494 (9)*
H11	0.4148	0.0471	0.2210	0.059*
C12	0.38527 (14)	0.13139 (18)	0.11560 (11)	0.0601 (10)*
H12	0.4023	0.0622	0.0897	0.072*
C13	0.35227 (15)	0.2438 (2)	0.07563 (9)	0.0608 (10)*
H13	0.3473	0.2499	0.0230	0.073*
C14	0.32675 (14)	0.34720 (18)	0.11434 (11)	0.0555 (10)*
H14	0.3047	0.4224	0.0876	0.067*
C15	0.33423 (13)	0.33813 (17)	0.19302 (11)	0.0466 (8)*
H15	0.3172	0.4073	0.2189	0.056*
F1	0.22629 (14)	0.3231 (3)	0.40751 (14)	0.0835 (8)
F2	0.21566 (12)	0.3449 (2)	0.28749 (13)	0.0669 (6)
F3	0.23022 (15)	0.1547 (2)	0.33774 (16)	0.0993 (9)
F4	0.37300 (14)	0.3145 (2)	0.50066 (12)	0.0754 (7)
F5	0.46835 (15)	0.2270 (2)	0.46033 (12)	0.0800 (8)
F6	0.35961 (17)	0.1182 (2)	0.45739 (13)	0.0893 (8)
N1	0.37711 (18)	0.2064 (3)	0.31227 (16)	0.0524 (8)
H1	0.4028	0.1363	0.3315	0.063*
N2	0.4705 (3)	0.8162 (4)	0.3508 (2)	0.0734 (11)
O1	0.4272 (2)	0.9060 (3)	0.3610 (2)	0.1023 (12)
O2	0.5363 (3)	0.8262 (3)	0.3361 (2)	0.1102 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (2)	0.045 (2)	0.0416 (19)	−0.0017 (17)	0.0125 (16)	0.0008 (16)
C2	0.060 (3)	0.062 (3)	0.060 (3)	−0.017 (2)	0.013 (2)	0.004 (2)
C3	0.071 (3)	0.055 (3)	0.052 (2)	−0.004 (2)	0.019 (2)	0.0064 (19)
F1	0.0631 (15)	0.119 (2)	0.0793 (17)	−0.0135 (14)	0.0382 (13)	0.0020 (15)
F2	0.0483 (12)	0.0805 (16)	0.0666 (15)	−0.0056 (11)	0.0052 (10)	0.0001 (12)
F3	0.0873 (19)	0.0665 (17)	0.138 (2)	−0.0374 (14)	0.0173 (17)	0.0034 (15)
F4	0.0944 (18)	0.0894 (17)	0.0450 (13)	−0.0027 (13)	0.0228 (12)	−0.0045 (12)
F5	0.0720 (17)	0.106 (2)	0.0585 (15)	0.0181 (14)	0.0099 (12)	0.0254 (13)
F6	0.132 (2)	0.0660 (17)	0.0684 (16)	−0.0157 (15)	0.0235 (15)	0.0231 (12)
N1	0.075 (2)	0.0340 (16)	0.0484 (17)	0.0132 (15)	0.0158 (15)	0.0047 (13)
N2	0.094 (3)	0.047 (2)	0.065 (2)	−0.018 (2)	−0.005 (2)	0.0112 (18)
O1	0.138 (3)	0.0375 (17)	0.118 (3)	0.001 (2)	0.007 (2)	0.0038 (18)
O2	0.101 (3)	0.080 (2)	0.144 (3)	−0.042 (2)	0.022 (2)	0.026 (2)

Geometric parameters (Å, º) top

C1—N1	1.434 (4)	C8—C9	1.3900
C1—C4	1.531 (4)	C8—H8	0.9300
C1—C3	1.538 (5)	C9—H9	0.9300
C1—C2	1.558 (5)	C10—C11	1.3900
C2—F2	1.328 (4)	C10—C15	1.3900
C2—F3	1.327 (4)	C10—N1	1.405 (3)
C2—F1	1.330 (4)	C11—C12	1.3900
C3—F5	1.325 (4)	C11—H11	0.9300
C3—F4	1.325 (4)	C12—C13	1.3900
C3—F6	1.331 (4)	C12—H12	0.9300
C4—C5	1.3900	C13—C14	1.3900
C4—C9	1.3900	C13—H13	0.9300
C5—C6	1.3900	C14—C15	1.3900
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.3900	C15—H15	0.9300
C6—H6	0.9300	N1—H1	0.8600
C7—C8	1.3900	N2—O2	1.212 (5)
C7—N2	1.462 (4)	N2—O1	1.215 (5)

N1—C1—C4	112.1 (2)	C7—C8—C9	120.0
N1—C1—C3	107.3 (3)	C7—C8—H8	120.0
C4—C1—C3	106.9 (3)	C9—C8—H8	120.0
N1—C1—C2	109.7 (3)	C8—C9—C4	120.0
C4—C1—C2	112.9 (3)	C8—C9—H9	120.0
C3—C1—C2	107.7 (3)	C4—C9—H9	120.0
F2—C2—F3	106.2 (3)	C11—C10—C15	120.0
F2—C2—F1	106.4 (3)	C11—C10—N1	115.49 (17)
F3—C2—F1	106.9 (3)	C15—C10—N1	124.51 (17)
F2—C2—C1	112.2 (3)	C12—C11—C10	120.0
F3—C2—C1	111.0 (3)	C12—C11—H11	120.0
F1—C2—C1	113.6 (3)	C10—C11—H11	120.0
F5—C3—F4	106.6 (3)	C11—C12—C13	120.0
F5—C3—F6	107.0 (3)	C11—C12—H12	120.0
F4—C3—F6	107.1 (3)	C13—C12—H12	120.0
F5—C3—C1	111.3 (3)	C14—C13—C12	120.0
F4—C3—C1	112.4 (3)	C14—C13—H13	120.0
F6—C3—C1	112.1 (3)	C12—C13—H13	120.0
C5—C4—C9	120.0	C15—C14—C13	120.0
C5—C4—C1	117.09 (17)	C15—C14—H14	120.0
C9—C4—C1	122.91 (17)	C13—C14—H14	120.0
C6—C5—C4	120.0	C14—C15—C10	120.0
C6—C5—H5	120.0	C14—C15—H15	120.0
C4—C5—H5	120.0	C10—C15—H15	120.0
C7—C6—C5	120.0	C10—N1—C1	127.9 (3)
C7—C6—H6	120.0	C10—N1—H1	116.1
C5—C6—H6	120.0	C1—N1—H1	116.1
C8—C7—C6	120.0	O2—N2—O1	126.4 (4)
C8—C7—N2	120.2 (2)	O2—N2—C7	117.3 (4)
C6—C7—N2	119.7 (2)	O1—N2—C7	116.3 (4)

N1—C1—C2—F2	−76.1 (4)	C4—C5—C6—C7	0.0
C4—C1—C2—F2	49.6 (4)	C5—C6—C7—C8	0.0
C3—C1—C2—F2	167.4 (3)	C5—C6—C7—N2	−178.1 (2)
N1—C1—C2—F3	42.6 (4)	C6—C7—C8—C9	0.0
C4—C1—C2—F3	168.3 (3)	N2—C7—C8—C9	178.1 (2)
C3—C1—C2—F3	−73.9 (4)	C7—C8—C9—C4	0.0
N1—C1—C2—F1	163.1 (3)	C5—C4—C9—C8	0.0
C4—C1—C2—F1	−71.2 (4)	C1—C4—C9—C8	−179.5 (2)
C3—C1—C2—F1	46.6 (4)	C15—C10—C11—C12	0.0
N1—C1—C3—F5	53.9 (4)	N1—C10—C11—C12	179.7 (2)
C4—C1—C3—F5	−66.4 (4)	C10—C11—C12—C13	0.0
C2—C1—C3—F5	172.0 (3)	C11—C12—C13—C14	0.0
N1—C1—C3—F4	173.5 (3)	C12—C13—C14—C15	0.0
C4—C1—C3—F4	53.1 (4)	C13—C14—C15—C10	0.0
C2—C1—C3—F4	−68.5 (4)	C11—C10—C15—C14	0.0
N1—C1—C3—F6	−65.9 (4)	N1—C10—C15—C14	−179.7 (2)
C4—C1—C3—F6	173.7 (3)	C11—C10—N1—C1	−173.5 (3)
C2—C1—C3—F6	52.2 (4)	C15—C10—N1—C1	6.2 (4)
N1—C1—C4—C5	−34.4 (3)	C4—C1—N1—C10	−53.8 (4)
C3—C1—C4—C5	82.9 (3)	C3—C1—N1—C10	−170.8 (3)
C2—C1—C4—C5	−158.9 (2)	C2—C1—N1—C10	72.5 (4)
N1—C1—C4—C9	145.1 (2)	C8—C7—N2—O2	−177.0 (3)
C3—C1—C4—C9	−97.6 (3)	C6—C7—N2—O2	1.1 (4)
C2—C1—C4—C9	20.6 (3)	C8—C7—N2—O1	2.8 (4)
C9—C4—C5—C6	0.0	C6—C7—N2—O1	−179.1 (3)
C1—C4—C5—C6	179.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.42	3.234 (4)	159

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀F₆N₂O₂
M_r	364.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	16.903 (3), 10.182 (2), 17.971 (3)
β (°)	104.90 (1)
V (Å³)	2989.1 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.40 × 0.35 × 0.25

Data collection
Diffractometer	Picker four-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7110, 3603, 1373
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.173, 0.98
No. of reflections	3603
No. of parameters	143
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.26

Computer programs: XSTAL (Brown, 1985), a modification of Picker FACS-I software (Picker, 1967), CELL (Brown, 1985), MINCON (Brown, 1985), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).