(4-Chloro-2-fluoro-phen-yl)[1-(2,6-difluoro-phen-yl)but-3-en-yl]amine.

In the mol-ecule of the title homoallylic amine, C(16)H(13)ClF(3)N, the dihedral angle between the two benzene rings is 84.63 (4)°. Weak intra-molecular N-H⋯F hydrogen bonds generate S(6) and S(5) ring motifs. In the crystal structure, weak inter-molecuar N-H⋯F hydrogen bonds link mol-ecules into centrosymmetric dimers which are arranged in mol-ecular sheets parallel to the ac plane.

Related literature

For standard bond lengths, see Allen et al. (1987 ▶). For hydrogen-bond motifs, see Bernstein et al. (1995 ▶). For background to the bioactivity and applications of homoallylic amines, see: Edwards et al. (1998 ▶); Robert (1998 ▶); Sabine & Horst (1991 ▶); Xie et al. (1989 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C16H13ClF3N

M = 311.72

Monoclinic,

a = 10.8980 (1) Å

b = 14.0073 (2) Å

c = 10.1651 (1) Å

β = 113.018 (1)°

V = 1428.17 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 100 K

0.50 × 0.39 × 0.27 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.868, T max = 0.926

32850 measured reflections

7434 independent reflections

6099 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.119

S = 1.04

7434 reflections

202 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.63 e Å−3

Δρmin = −0.86 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012896/lh2803sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012896/lh2803Isup2.hkl

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

C16H13ClF3N	F(000) = 640
Mr = 311.72	Dx = 1.450 Mg m−3
Monoclinic, P21/c	Melting point = 399–400 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.8980 (1) Å	Cell parameters from 7434 reflections
b = 14.0073 (2) Å	θ = 2.0–37.5°
c = 10.1651 (1) Å	µ = 0.29 mm−1
β = 113.018 (1)°	T = 100 K
V = 1428.17 (3) Å3	Block, colorless
Z = 4	0.50 × 0.39 × 0.27 mm

Bruker APEXII CCD area-detector diffractometer	7434 independent reflections
Radiation source: sealed tube	6099 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 37.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→18
Tmin = 0.868, Tmax = 0.926	k = −22→23
32850 measured reflections	l = −17→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.059P)2 + 0.3248P] where P = (Fo2 + 2Fc2)/3
7434 reflections	(Δ/σ)max = 0.001
202 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.85 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
Cl1	0.35924 (3)	0.625873 (17)	1.05066 (4)	0.03621 (8)
F1	0.89730 (5)	0.44888 (4)	0.88286 (5)	0.02227 (11)
F2	0.65542 (6)	0.64050 (4)	0.48567 (6)	0.02478 (12)
F3	0.85689 (7)	0.60562 (5)	1.18096 (6)	0.03051 (13)
N1	0.84154 (7)	0.64304 (5)	0.91602 (7)	0.01799 (11)
C1	0.59745 (8)	0.65594 (6)	0.83617 (9)	0.01870 (13)
H1A	0.5873	0.6695	0.7429	0.022*
C2	0.48485 (9)	0.65290 (6)	0.86995 (10)	0.02241 (15)
H2A	0.4007	0.6643	0.7996	0.027*
C3	0.49921 (10)	0.63283 (6)	1.00871 (11)	0.02434 (16)
C4	0.62453 (11)	0.61733 (6)	1.11567 (10)	0.02539 (17)
H4A	0.6347	0.6051	1.2093	0.030*
C5	0.73310 (9)	0.62070 (6)	1.07837 (9)	0.02114 (14)
C6	0.72486 (8)	0.63897 (5)	0.93977 (8)	0.01658 (12)
C7	0.84187 (7)	0.64023 (5)	0.77318 (8)	0.01602 (12)
H7A	0.7900	0.6949	0.7199	0.019*
C8	0.78026 (7)	0.55017 (5)	0.68918 (7)	0.01418 (11)
C9	0.69022 (8)	0.55353 (5)	0.54747 (8)	0.01668 (12)
C10	0.63233 (8)	0.47417 (6)	0.46594 (8)	0.01959 (13)
H10A	0.5721	0.4806	0.3717	0.024*
C11	0.66630 (9)	0.38468 (6)	0.52828 (9)	0.02012 (14)
H11A	0.6285	0.3303	0.4754	0.024*
C12	0.75652 (8)	0.37582 (5)	0.66927 (9)	0.01879 (13)
H12A	0.7801	0.3161	0.7117	0.023*
C13	0.81007 (7)	0.45824 (5)	0.74445 (8)	0.01578 (12)
C14	0.98669 (8)	0.65337 (6)	0.78678 (9)	0.02065 (14)
H14A	1.0232	0.7107	0.8416	0.025*
H14B	1.0396	0.5996	0.8389	0.025*
C15	0.99758 (9)	0.66087 (6)	0.64501 (10)	0.02264 (15)
H15A	0.9501	0.7093	0.5836	0.027*
C16	1.06994 (12)	0.60355 (8)	0.60087 (13)	0.0329 (2)
H1N1	0.9099 (16)	0.6141 (10)	0.9828 (17)	0.033 (4)*
H16B	1.1209 (16)	0.5526 (12)	0.6600 (17)	0.041 (4)*
H16A	1.0756 (18)	0.6098 (12)	0.513 (2)	0.049 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.04381 (15)	0.02600 (11)	0.05793 (18)	−0.00690 (9)	0.04060 (14)	−0.00647 (10)
F1	0.0223 (2)	0.0231 (2)	0.0163 (2)	0.00354 (17)	0.00191 (17)	0.00387 (17)
F2	0.0323 (3)	0.0181 (2)	0.0175 (2)	0.00117 (18)	0.0027 (2)	0.00436 (17)
F3	0.0343 (3)	0.0376 (3)	0.0167 (2)	0.0065 (2)	0.0068 (2)	0.0050 (2)
N1	0.0171 (3)	0.0222 (3)	0.0138 (2)	0.0005 (2)	0.0051 (2)	−0.0018 (2)
C1	0.0189 (3)	0.0205 (3)	0.0177 (3)	−0.0013 (2)	0.0083 (2)	−0.0033 (2)
C2	0.0216 (4)	0.0214 (3)	0.0271 (4)	−0.0026 (3)	0.0127 (3)	−0.0062 (3)
C3	0.0312 (4)	0.0177 (3)	0.0338 (4)	−0.0045 (3)	0.0233 (4)	−0.0050 (3)
C4	0.0398 (5)	0.0197 (3)	0.0243 (4)	−0.0011 (3)	0.0208 (4)	0.0002 (3)
C5	0.0286 (4)	0.0187 (3)	0.0172 (3)	0.0009 (3)	0.0101 (3)	0.0003 (2)
C6	0.0199 (3)	0.0149 (3)	0.0159 (3)	−0.0008 (2)	0.0080 (2)	−0.0023 (2)
C7	0.0162 (3)	0.0165 (3)	0.0151 (3)	−0.0012 (2)	0.0059 (2)	−0.0011 (2)
C8	0.0144 (3)	0.0153 (3)	0.0132 (3)	0.0001 (2)	0.0057 (2)	0.0001 (2)
C9	0.0193 (3)	0.0159 (3)	0.0141 (3)	0.0004 (2)	0.0057 (2)	0.0012 (2)
C10	0.0214 (3)	0.0205 (3)	0.0148 (3)	−0.0019 (2)	0.0049 (2)	−0.0024 (2)
C11	0.0224 (3)	0.0178 (3)	0.0206 (3)	−0.0028 (2)	0.0089 (3)	−0.0038 (2)
C12	0.0209 (3)	0.0155 (3)	0.0213 (3)	0.0006 (2)	0.0096 (3)	0.0007 (2)
C13	0.0148 (3)	0.0177 (3)	0.0146 (3)	0.0016 (2)	0.0054 (2)	0.0019 (2)
C14	0.0166 (3)	0.0239 (3)	0.0214 (3)	−0.0038 (2)	0.0075 (3)	−0.0009 (3)
C15	0.0211 (3)	0.0241 (3)	0.0254 (4)	−0.0005 (3)	0.0120 (3)	0.0054 (3)
C16	0.0365 (5)	0.0360 (5)	0.0357 (5)	0.0056 (4)	0.0245 (4)	0.0063 (4)

Cl1—C3	1.7398 (9)	C7—H7A	0.9800
F1—C13	1.3618 (9)	C8—C9	1.3910 (10)
F2—C9	1.3550 (9)	C8—C13	1.3915 (10)
F3—C5	1.3608 (11)	C9—C10	1.3826 (11)
N1—C6	1.3851 (11)	C10—C11	1.3879 (11)
N1—C7	1.4539 (10)	C10—H10A	0.9300
N1—H1N1	0.886 (16)	C11—C12	1.3907 (12)
C1—C6	1.3964 (11)	C11—H11A	0.9300
C1—C2	1.3983 (12)	C12—C13	1.3816 (11)
C1—H1A	0.9300	C12—H12A	0.9300
C2—C3	1.3857 (14)	C14—C15	1.4953 (12)
C2—H2A	0.9300	C14—H14A	0.9700
C3—C4	1.3904 (15)	C14—H14B	0.9700
C4—C5	1.3773 (13)	C15—C16	1.3208 (14)
C4—H4A	0.9300	C15—H15A	0.9300
C5—C6	1.3999 (11)	C16—H16B	0.958 (17)
C7—C8	1.5242 (10)	C16—H16A	0.924 (19)
C7—C14	1.5406 (11)
C6—N1—C7	122.26 (7)	C13—C8—C7	123.88 (6)
C6—N1—H1N1	113.7 (10)	F2—C9—C10	117.74 (7)
C7—N1—H1N1	115.1 (10)	F2—C9—C8	117.83 (6)
C6—C1—C2	121.26 (8)	C10—C9—C8	124.42 (7)
C6—C1—H1A	119.4	C9—C10—C11	118.34 (7)
C2—C1—H1A	119.4	C9—C10—H10A	120.8
C3—C2—C1	119.70 (9)	C11—C10—H10A	120.8
C3—C2—H2A	120.2	C10—C11—C12	120.40 (7)
C1—C2—H2A	120.2	C10—C11—H11A	119.8
C2—C3—C4	120.87 (8)	C12—C11—H11A	119.8
C2—C3—Cl1	120.00 (8)	C13—C12—C11	118.10 (7)
C4—C3—Cl1	119.13 (7)	C13—C12—H12A	120.9
C5—C4—C3	117.80 (8)	C11—C12—H12A	120.9
C5—C4—H4A	121.1	F1—C13—C12	117.66 (7)
C3—C4—H4A	121.1	F1—C13—C8	117.69 (7)
F3—C5—C4	118.99 (8)	C12—C13—C8	124.64 (7)
F3—C5—C6	116.99 (8)	C15—C14—C7	112.74 (7)
C4—C5—C6	124.01 (8)	C15—C14—H14A	109.0
N1—C6—C1	124.85 (7)	C7—C14—H14A	109.0
N1—C6—C5	118.75 (7)	C15—C14—H14B	109.0
C1—C6—C5	116.34 (8)	C7—C14—H14B	109.0
N1—C7—C8	114.16 (6)	H14A—C14—H14B	107.8
N1—C7—C14	108.04 (6)	C16—C15—C14	124.58 (9)
C8—C7—C14	111.13 (6)	C16—C15—H15A	117.7
N1—C7—H7A	107.8	C14—C15—H15A	117.7
C8—C7—H7A	107.8	C15—C16—H16B	121.1 (10)
C14—C7—H7A	107.8	C15—C16—H16A	123.1 (11)
C9—C8—C13	114.10 (6)	H16B—C16—H16A	115.8 (14)
C9—C8—C7	122.01 (6)
C6—C1—C2—C3	0.07 (12)	N1—C7—C8—C13	−47.16 (10)
C1—C2—C3—C4	1.19 (12)	C14—C7—C8—C13	75.34 (9)
C1—C2—C3—Cl1	−178.34 (6)	C13—C8—C9—F2	179.74 (7)
C2—C3—C4—C5	−1.30 (12)	C7—C8—C9—F2	−1.57 (11)
Cl1—C3—C4—C5	178.24 (6)	C13—C8—C9—C10	0.69 (11)
C3—C4—C5—F3	−179.88 (7)	C7—C8—C9—C10	179.38 (7)
C3—C4—C5—C6	0.17 (13)	F2—C9—C10—C11	−179.51 (8)
C7—N1—C6—C1	−16.99 (11)	C8—C9—C10—C11	−0.46 (13)
C7—N1—C6—C5	165.95 (7)	C9—C10—C11—C12	−0.06 (13)
C2—C1—C6—N1	−178.25 (7)	C10—C11—C12—C13	0.28 (12)
C2—C1—C6—C5	−1.12 (11)	C11—C12—C13—F1	179.36 (7)
F3—C5—C6—N1	−1.62 (11)	C11—C12—C13—C8	−0.01 (12)
C4—C5—C6—N1	178.32 (8)	C9—C8—C13—F1	−179.82 (6)
F3—C5—C6—C1	−178.93 (7)	C7—C8—C13—F1	1.51 (11)
C4—C5—C6—C1	1.02 (12)	C9—C8—C13—C12	−0.44 (11)
C6—N1—C7—C8	−59.79 (9)	C7—C8—C13—C12	−179.11 (7)
C6—N1—C7—C14	176.04 (7)	N1—C7—C14—C15	−174.60 (7)
N1—C7—C8—C9	134.28 (7)	C8—C7—C14—C15	59.43 (9)
C14—C7—C8—C9	−103.22 (8)	C7—C14—C15—C16	−122.17 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···F1	0.886 (17)	2.510 (14)	2.8354 (9)	102.4 (11)
N1—H1N1···F3	0.886 (17)	2.306 (17)	2.6839 (9)	105.7 (14)
N1—H1N1···F1i	0.886 (17)	2.194 (17)	3.0639 (9)	167.1 (16)
C7—H7A···F2	0.98	2.38	2.8330 (10)	107

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯F1	0.886 (17)	2.510 (14)	2.8354 (9)	102.4 (11)
N1—H1N1⋯F3	0.886 (17)	2.306 (17)	2.6839 (9)	105.7 (14)
N1—H1N1⋯F1i	0.886 (17)	2.194 (17)	3.0639 (9)	167.1 (16)
C7—H7A⋯F2	0.98	2.38	2.8330 (10)	107

Symmetry code: (i) .