Diethyl 2-{[2-(trifluoro-meth-yl)anil-ino]methyl-idene}propane-dioate.

The title compound, C(15)H(16)F(3)NO(4), is an N-substituted derivative of ortho-trifluoro-methyl-aniline featuring a twofold Michael system. The least-squares planes defined by the atoms of the phenyl ring and the atoms of the Michael system enclose an angle of 15.52 (5)°. Apart from classical intra-molecular N-H⋯O and N-H⋯F hydrogen bonds, inter-molecular C-H⋯O contacts are observed, the latter connecting the mol-ecules into chains along [110]. The shortest inter-centroid distance between two aromatic systems is 3.6875 (9) Å.

Related literature

For the crystal structure of another ortho-trifluoro­methyl aniline derivative featuring a Michael system as substituent, see: Schweinfurth et al. (2011 ▶). For general information on Michael systems, see: McMurry (1992 ▶). For general pharmaceutical background to derivatives of the title compound, see: Kaur et al. (2010 ▶); Eswaran et al. (2010 ▶); Chou et al. (2010 ▶); Chen et al. (2004 ▶); Shingalapur et al. (2009 ▶). For the preparation of the title compound, see: Eswaran et al. (2009 ▶) For the graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C15H16F3NO4

M = 331.29

Triclinic,

a = 7.8080 (2) Å

b = 10.1485 (3) Å

c = 10.5265 (3) Å

α = 95.193 (1)°

β = 109.183 (1)°

γ = 99.405 (1)°

V = 767.84 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 200 K

0.55 × 0.39 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.946, T max = 1.000

13616 measured reflections

3825 independent reflections

3240 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.128

S = 1.05

3825 reflections

210 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812002590/bg2441sup1.cif

Supplementary material file. DOI: 10.1107/S1600536812002590/bg2441Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002590/bg2441Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536812002590/bg2441Isup4.cml

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

C15H16F3NO4	Z = 2
Mr = 331.29	F(000) = 344
Triclinic, P1	Dx = 1.433 Mg m−3
Hall symbol: -P 1	Melting point: 357(1) K
a = 7.8080 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1485 (3) Å	Cell parameters from 7916 reflections
c = 10.5265 (3) Å	θ = 2.8–28.3°
α = 95.193 (1)°	µ = 0.13 mm−1
β = 109.183 (1)°	T = 200 K
γ = 99.405 (1)°	Platelet, colourless
V = 767.84 (4) Å3	0.55 × 0.39 × 0.09 mm

Bruker APEXII CCD diffractometer	3825 independent reflections
Radiation source: fine-focus sealed tube	3240 reflections with I > 2σ(I)
graphite	Rint = 0.014
φ and ω scans	θmax = 28.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
Tmin = 0.946, Tmax = 1.000	k = −13→13
13616 measured reflections	l = −14→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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0646P)2 + 0.2686P] where P = (Fo2 + 2Fc2)/3
3825 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

	x	y	z	Uiso*/Ueq
F1	0.3636 (2)	−0.04352 (13)	0.35986 (11)	0.0857 (5)
F2	0.3880 (2)	0.16548 (13)	0.34858 (11)	0.0744 (4)
F3	0.60489 (16)	0.07240 (15)	0.33735 (11)	0.0755 (4)
O1	0.86819 (16)	0.61635 (10)	0.03165 (10)	0.0418 (3)
O2	0.68442 (13)	0.44254 (9)	−0.12584 (9)	0.0335 (2)
O3	0.71583 (16)	0.42107 (11)	0.32438 (10)	0.0431 (3)
O4	0.82996 (15)	0.61975 (10)	0.27787 (9)	0.0374 (2)
N1	0.49938 (14)	0.23376 (10)	0.11834 (10)	0.0264 (2)
H1	0.5378	0.2582	0.2071	0.032*
C1	0.36699 (16)	0.11270 (12)	0.06191 (12)	0.0251 (2)
C2	0.32968 (18)	0.02013 (13)	0.14539 (13)	0.0295 (3)
C3	0.20078 (19)	−0.10035 (13)	0.08848 (15)	0.0345 (3)
H3	0.1757	−0.1621	0.1459	0.041*
C4	0.10908 (19)	−0.13115 (13)	−0.05021 (15)	0.0360 (3)
H4	0.0239	−0.2147	−0.0890	0.043*
C5	0.1430 (2)	−0.03872 (15)	−0.13194 (15)	0.0376 (3)
H5	0.0788	−0.0587	−0.2275	0.045*
C6	0.26878 (19)	0.08245 (14)	−0.07735 (13)	0.0335 (3)
H6	0.2882	0.1454	−0.1353	0.040*
C7	0.4211 (2)	0.05075 (16)	0.29631 (15)	0.0439 (4)
C8	0.57087 (16)	0.31427 (12)	0.04683 (12)	0.0247 (2)
H8	0.5348	0.2837	−0.0480	0.030*
C9	0.69146 (16)	0.43685 (12)	0.09707 (12)	0.0246 (2)
C10	0.75905 (16)	0.51016 (12)	0.00254 (12)	0.0263 (2)
C11	0.7483 (2)	0.50110 (15)	−0.22660 (14)	0.0353 (3)
H11A	0.8853	0.5197	−0.1952	0.042*
H11B	0.7065	0.5872	−0.2421	0.042*
C12	0.6691 (3)	0.4020 (2)	−0.35413 (17)	0.0588 (5)
H12A	0.5338	0.3800	−0.3810	0.088*
H12B	0.7180	0.3196	−0.3391	0.088*
H12C	0.7030	0.4411	−0.4265	0.088*
C13	0.74669 (17)	0.48967 (13)	0.24184 (13)	0.0287 (3)
C14	0.8920 (2)	0.67197 (15)	0.42245 (14)	0.0432 (4)
H14A	1.0000	0.6351	0.4733	0.052*
H14B	0.7915	0.6459	0.4588	0.052*
C15	0.9441 (4)	0.82171 (18)	0.43692 (19)	0.0652 (6)
H15A	1.0332	0.8459	0.3913	0.098*
H15B	1.0003	0.8600	0.5337	0.098*
H15C	0.8332	0.8578	0.3953	0.098*

	U11	U22	U33	U12	U13	U23
F1	0.1160 (11)	0.0754 (8)	0.0410 (6)	−0.0340 (7)	0.0158 (6)	0.0275 (6)
F2	0.1112 (10)	0.0703 (8)	0.0401 (6)	0.0085 (7)	0.0324 (6)	−0.0040 (5)
F3	0.0501 (6)	0.1190 (11)	0.0426 (6)	0.0030 (6)	−0.0001 (5)	0.0263 (6)
O1	0.0542 (6)	0.0302 (5)	0.0357 (5)	−0.0117 (4)	0.0186 (5)	0.0039 (4)
O2	0.0392 (5)	0.0344 (5)	0.0256 (4)	−0.0053 (4)	0.0160 (4)	0.0038 (4)
O3	0.0599 (7)	0.0368 (5)	0.0243 (5)	−0.0072 (5)	0.0115 (4)	0.0062 (4)
O4	0.0508 (6)	0.0286 (5)	0.0254 (5)	−0.0056 (4)	0.0111 (4)	0.0000 (4)
N1	0.0288 (5)	0.0256 (5)	0.0226 (5)	−0.0010 (4)	0.0092 (4)	0.0048 (4)
C1	0.0255 (5)	0.0230 (5)	0.0274 (6)	0.0017 (4)	0.0115 (4)	0.0046 (4)
C2	0.0320 (6)	0.0278 (6)	0.0307 (6)	0.0035 (5)	0.0137 (5)	0.0088 (5)
C3	0.0378 (7)	0.0252 (6)	0.0434 (7)	0.0022 (5)	0.0186 (6)	0.0106 (5)
C4	0.0340 (6)	0.0251 (6)	0.0459 (8)	−0.0017 (5)	0.0156 (6)	−0.0011 (5)
C5	0.0372 (7)	0.0377 (7)	0.0313 (7)	−0.0039 (6)	0.0108 (5)	−0.0015 (5)
C6	0.0350 (6)	0.0341 (7)	0.0278 (6)	−0.0034 (5)	0.0112 (5)	0.0058 (5)
C7	0.0511 (8)	0.0435 (8)	0.0324 (7)	−0.0059 (6)	0.0140 (6)	0.0135 (6)
C8	0.0260 (5)	0.0246 (5)	0.0245 (5)	0.0034 (4)	0.0108 (4)	0.0051 (4)
C9	0.0265 (5)	0.0236 (5)	0.0239 (6)	0.0030 (4)	0.0098 (4)	0.0050 (4)
C10	0.0282 (5)	0.0247 (5)	0.0270 (6)	0.0036 (4)	0.0111 (5)	0.0061 (4)
C11	0.0411 (7)	0.0387 (7)	0.0315 (7)	0.0042 (6)	0.0197 (6)	0.0133 (5)
C12	0.0817 (13)	0.0610 (11)	0.0340 (8)	−0.0048 (9)	0.0308 (9)	0.0038 (7)
C13	0.0301 (6)	0.0277 (6)	0.0254 (6)	0.0014 (5)	0.0080 (5)	0.0046 (5)
C14	0.0556 (9)	0.0387 (8)	0.0251 (6)	−0.0028 (6)	0.0083 (6)	−0.0011 (5)
C15	0.1017 (16)	0.0404 (9)	0.0358 (8)	−0.0061 (9)	0.0137 (9)	−0.0067 (7)

F1—C7	1.3179 (16)	C5—C6	1.3832 (18)
F2—C7	1.342 (2)	C5—H5	0.9500
F3—C7	1.329 (2)	C6—H6	0.9500
O1—C10	1.2042 (15)	C8—C9	1.3728 (16)
O2—C10	1.3492 (15)	C8—H8	0.9500
O2—C11	1.4464 (14)	C9—C13	1.4630 (17)
O3—C13	1.2207 (16)	C9—C10	1.4741 (16)
O4—C13	1.3327 (15)	C11—C12	1.484 (2)
O4—C14	1.4551 (16)	C11—H11A	0.9900
N1—C8	1.3357 (14)	C11—H11B	0.9900
N1—C1	1.4071 (15)	C12—H12A	0.9800
N1—H1	0.8800	C12—H12B	0.9800
C1—C6	1.3908 (17)	C12—H12C	0.9800
C1—C2	1.4029 (16)	C14—C15	1.488 (2)
C2—C3	1.3913 (18)	C14—H14A	0.9900
C2—C7	1.4909 (19)	C14—H14B	0.9900
C3—C4	1.378 (2)	C15—H15A	0.9800
C3—H3	0.9500	C15—H15B	0.9800
C4—C5	1.380 (2)	C15—H15C	0.9800
C4—H4	0.9500
C10—O2—C11	116.56 (10)	C8—C9—C10	118.54 (11)
C13—O4—C14	115.84 (10)	C13—C9—C10	122.74 (10)
C8—N1—C1	124.71 (10)	O1—C10—O2	122.13 (11)
C8—N1—H1	117.6	O1—C10—C9	126.34 (12)
C1—N1—H1	117.6	O2—C10—C9	111.52 (10)
C6—C1—C2	118.40 (11)	O2—C11—C12	107.34 (12)
C6—C1—N1	120.99 (11)	O2—C11—H11A	110.2
C2—C1—N1	120.61 (11)	C12—C11—H11A	110.2
C3—C2—C1	120.22 (12)	O2—C11—H11B	110.2
C3—C2—C7	118.76 (12)	C12—C11—H11B	110.2
C1—C2—C7	120.98 (11)	H11A—C11—H11B	108.5
C4—C3—C2	120.77 (12)	C11—C12—H12A	109.5
C4—C3—H3	119.6	C11—C12—H12B	109.5
C2—C3—H3	119.6	H12A—C12—H12B	109.5
C3—C4—C5	118.95 (12)	C11—C12—H12C	109.5
C3—C4—H4	120.5	H12A—C12—H12C	109.5
C5—C4—H4	120.5	H12B—C12—H12C	109.5
C4—C5—C6	121.24 (13)	O3—C13—O4	121.74 (12)
C4—C5—H5	119.4	O3—C13—C9	122.85 (11)
C6—C5—H5	119.4	O4—C13—C9	115.40 (10)
C5—C6—C1	120.37 (12)	O4—C14—C15	107.04 (12)
C5—C6—H6	119.8	O4—C14—H14A	110.3
C1—C6—H6	119.8	C15—C14—H14A	110.3
F1—C7—F3	108.38 (14)	O4—C14—H14B	110.3
F1—C7—F2	105.40 (15)	C15—C14—H14B	110.3
F3—C7—F2	103.63 (14)	H14A—C14—H14B	108.6
F1—C7—C2	113.24 (13)	C14—C15—H15A	109.5
F3—C7—C2	113.39 (13)	C14—C15—H15B	109.5
F2—C7—C2	112.06 (13)	H15A—C15—H15B	109.5
N1—C8—C9	126.33 (11)	C14—C15—H15C	109.5
N1—C8—H8	116.8	H15A—C15—H15C	109.5
C9—C8—H8	116.8	H15B—C15—H15C	109.5
C8—C9—C13	118.72 (10)
C8—N1—C1—C6	−14.70 (19)	C1—C2—C7—F2	57.59 (18)
C8—N1—C1—C2	165.95 (11)	C1—N1—C8—C9	175.78 (12)
C6—C1—C2—C3	1.70 (19)	N1—C8—C9—C13	−1.73 (19)
N1—C1—C2—C3	−178.93 (11)	N1—C8—C9—C10	178.62 (11)
C6—C1—C2—C7	−175.94 (13)	C11—O2—C10—O1	2.65 (19)
N1—C1—C2—C7	3.43 (19)	C11—O2—C10—C9	−176.71 (10)
C1—C2—C3—C4	0.5 (2)	C8—C9—C10—O1	−177.98 (13)
C7—C2—C3—C4	178.20 (13)	C13—C9—C10—O1	2.4 (2)
C2—C3—C4—C5	−1.9 (2)	C8—C9—C10—O2	1.34 (16)
C3—C4—C5—C6	1.0 (2)	C13—C9—C10—O2	−178.29 (11)
C4—C5—C6—C1	1.2 (2)	C10—O2—C11—C12	172.35 (13)
C2—C1—C6—C5	−2.6 (2)	C14—O4—C13—O3	3.8 (2)
N1—C1—C6—C5	178.08 (12)	C14—O4—C13—C9	−177.67 (12)
C3—C2—C7—F1	−1.0 (2)	C8—C9—C13—O3	12.48 (19)
C1—C2—C7—F1	176.66 (14)	C10—C9—C13—O3	−167.89 (13)
C3—C2—C7—F3	123.02 (15)	C8—C9—C13—O4	−166.01 (11)
C1—C2—C7—F3	−59.31 (19)	C10—C9—C13—O4	13.62 (18)
C3—C2—C7—F2	−120.09 (15)	C13—O4—C14—C15	−168.58 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F2	0.88	2.35	2.9330 (15)	124
N1—H1···F3	0.88	2.45	2.9242 (15)	114
N1—H1···O3	0.88	1.99	2.6399 (14)	130
C3—H3···F1	0.95	2.33	2.6805 (19)	101
C4—H4···O1i	0.95	2.60	3.2766 (17)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯F2	0.88	2.35	2.9330 (15)	124
N1—H1⋯F3	0.88	2.45	2.9242 (15)	114
N1—H1⋯O3	0.88	1.99	2.6399 (14)	130
C4—H4⋯O1i	0.95	2.60	3.2766 (17)	129

Symmetry code: (i) .