Crystal structure of (Z)-3-[5-chloro-2-(prop-2-yn-yloxy)phen-yl]-3-hy-droxy-1-[4-(tri-fluoro-meth-yl)phen-yl]-prop-2-en-1-one.

The title compound, C19H12ClF3O3, obtained by the photochemical transformation of 2-[5-chloro-2-(prop-2-yn-yloxy)benzo-yl]-3-[4-(tri-fluoro-meth-yl)phen-yl]oxirane adopts a Z conformation with respect to the enolic C=C double bond. The dihedral angle between the benzene rings is 12.25 (16)° and an intra-molecular O-H⋯O hydrogen bond closes an S(6) ring. An intra-molecular C-H⋯O inter-action also leads to an S(6) ring. In the crystal, very weak C-H⋯O inter-actions and short Cl⋯Cl contacts [3.3221 (16) Å] are seen, as well as weak aromatic π-π stacking inter-actions [centroid-centroid separation = 3.879 (2) Å].

Related literature

For background to 1,3-diketones, see: Andrae et al. (1997 ▸); Crouse et al. (1989 ▸); Diana et al. (1978 ▸); Nishiyama et al. (2002 ▸); Sheikh et al. (2009 ▸, 2013 ▸); Tchertanov & Mouscadet (2007 ▸).

Experimental

Crystal data

C19H12ClF3O3

M = 380.74

Triclinic,

a = 8.2203 (12) Å

b = 9.3822 (14) Å

c = 12.3140 (18) Å

α = 90.150 (2)°

β = 109.201 (2)°

γ = 106.212 (2)°

V = 856.5 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 273 K

0.34 × 0.29 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T min = 0.912, T max = 0.962

8272 measured reflections

3016 independent reflections

2503 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.191

S = 1.10

3003 reflections

235 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.35 e Å−3

Data collection: SMART (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); 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: SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015012748/hb7451sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012748/hb7451Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015012748/hb7451Isup3.cml

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. DOI: 10.1107/S2056989015012748/hb7451fig1.tif

Mol­ecular structure of the title compound showing displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989015012748/hb7451fig2.tif

A view along the a axis of the inter- and intra­molecular hydrogen bonds in the title compound (shown as dashed lines, see Table 1 for details). Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

Click here for additional data file.

a . DOI: 10.1107/S2056989015012748/hb7451fig3.tif

A view along the a axis showing F⋯F and Cl⋯Cl contact distances (dashed lines). Hydrogen atoms not involved in the inter­actions are excluded for clarity.

Click here for additional data file.

b . DOI: 10.1107/S2056989015012748/hb7451fig4.tif

A partial view along b axis of the π–π inter­actions (dashed lines) in the crystal packing of the title compound. All hydrogen atoms are omitted for clarity.

CCDC reference: 1403411

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H12ClF3O3	Z = 2
Mr = 380.74	F(000) = 388.0
Triclinic, P1	Dx = 1.476 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2203 (12) Å	Cell parameters from 3035 reflections
b = 9.3822 (14) Å	θ = 2.3–25.6°
c = 12.3140 (18) Å	µ = 0.27 mm−1
α = 90.150 (2)°	T = 273 K
β = 109.201 (2)°	Block, colorless
γ = 106.212 (2)°	0.34 × 0.29 × 0.14 mm
V = 856.5 (2) Å3

Bruker SMART CCD diffractometer	3016 independent reflections
Radiation source: fine-focus sealed tube	2503 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
Tmin = 0.912, Tmax = 0.962	k = −11→11
8272 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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0963P)2 + 0.390P] where P = (Fo2 + 2Fc2)/3
3003 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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	0.10694 (14)	1.10578 (13)	1.42182 (7)	0.0913 (4)
O3	0.2888 (3)	1.16996 (19)	0.99885 (16)	0.0600 (5)
O2	0.1279 (3)	0.7541 (2)	1.1146 (2)	0.0766 (7)
H24	0.1237	0.6813	1.0756	0.115*
C13	0.2457 (4)	0.7250 (3)	0.8037 (2)	0.0508 (6)
C12	0.2108 (4)	0.7295 (3)	0.9149 (2)	0.0525 (7)
C4	0.1949 (3)	1.0149 (3)	1.1317 (2)	0.0474 (6)
C2	0.1511 (4)	1.0020 (3)	1.2318 (2)	0.0558 (7)
H2	0.1147	0.9080	1.2557	0.067*
C6	0.2471 (3)	1.1588 (3)	1.0975 (2)	0.0485 (6)
C10	0.1852 (3)	0.8758 (3)	1.0691 (2)	0.0493 (6)
C11	0.2284 (4)	0.8668 (3)	0.9711 (2)	0.0531 (7)
H11	0.2707	0.9545	0.9408	0.064*
C15	0.3271 (4)	0.8532 (3)	0.7619 (3)	0.0585 (7)
H15	0.3643	0.9449	0.8054	0.070*
C18	0.3000 (4)	0.7117 (3)	0.5930 (2)	0.0575 (7)
C5	0.2558 (4)	1.2823 (3)	1.1638 (3)	0.0602 (7)
H5	0.2906	1.3771	1.1410	0.072*
C17	0.3537 (4)	0.8470 (3)	0.6579 (3)	0.0618 (7)
H17	0.4077	0.9339	0.6313	0.074*
C1	0.1610 (4)	1.1259 (4)	1.2959 (2)	0.0620 (8)
F3	0.4185 (4)	0.8295 (3)	0.4541 (2)	0.1194 (9)
C7	0.3400 (4)	1.3122 (3)	0.9602 (3)	0.0611 (7)
H7A	0.4485	1.3760	1.0179	0.073*
H7B	0.2448	1.3590	0.9473	0.073*
C14	0.1936 (4)	0.5899 (3)	0.7376 (3)	0.0633 (8)
H14	0.1400	0.5026	0.7641	0.076*
C3	0.2136 (4)	1.2658 (4)	1.2624 (3)	0.0656 (8)
H3	0.2204	1.3491	1.3067	0.079*
C8	0.3725 (5)	1.2911 (4)	0.8531 (3)	0.0750 (9)
C16	0.2202 (5)	0.5826 (3)	0.6329 (3)	0.0686 (8)
H16	0.1844	0.4911	0.5893	0.082*
C19	0.3237 (5)	0.7041 (4)	0.4781 (3)	0.0763 (9)
C9	0.3999 (8)	1.2763 (5)	0.7678 (4)	0.1171 (17)
H9	0.4219	1.2645	0.6994	0.140*
F2	0.1707 (4)	0.6729 (5)	0.3933 (2)	0.1649 (15)
F1	0.4002 (7)	0.6064 (4)	0.4652 (3)	0.1871 (19)
O1	0.1593 (3)	0.6070 (2)	0.9541 (2)	0.0759 (7)

	U11	U22	U33	U12	U13	U23
Cl1	0.0980 (7)	0.1272 (9)	0.0637 (6)	0.0341 (6)	0.0464 (5)	0.0084 (5)
O3	0.0908 (14)	0.0395 (10)	0.0603 (12)	0.0176 (9)	0.0411 (11)	0.0111 (8)
O2	0.1181 (19)	0.0490 (12)	0.0843 (15)	0.0281 (12)	0.0595 (14)	0.0234 (10)
C13	0.0497 (14)	0.0436 (14)	0.0584 (16)	0.0184 (11)	0.0138 (12)	0.0050 (12)
C12	0.0546 (15)	0.0452 (14)	0.0606 (16)	0.0198 (12)	0.0194 (13)	0.0107 (12)
C4	0.0428 (13)	0.0516 (15)	0.0478 (14)	0.0153 (11)	0.0147 (11)	0.0084 (11)
C2	0.0511 (15)	0.0652 (17)	0.0518 (15)	0.0155 (13)	0.0199 (12)	0.0142 (13)
C6	0.0479 (14)	0.0473 (14)	0.0502 (14)	0.0137 (11)	0.0168 (11)	0.0048 (11)
C10	0.0491 (14)	0.0440 (14)	0.0553 (15)	0.0151 (11)	0.0173 (12)	0.0134 (11)
C11	0.0618 (16)	0.0408 (14)	0.0579 (16)	0.0137 (12)	0.0235 (13)	0.0104 (12)
C15	0.0625 (17)	0.0463 (15)	0.0667 (18)	0.0101 (13)	0.0272 (14)	−0.0019 (13)
C18	0.0556 (16)	0.0593 (17)	0.0560 (16)	0.0204 (13)	0.0145 (13)	0.0020 (13)
C5	0.0659 (18)	0.0521 (16)	0.0641 (17)	0.0166 (13)	0.0252 (15)	0.0005 (13)
C17	0.0632 (17)	0.0519 (16)	0.0696 (19)	0.0092 (13)	0.0284 (15)	0.0047 (14)
C1	0.0552 (16)	0.084 (2)	0.0492 (15)	0.0215 (15)	0.0204 (13)	0.0054 (14)
F3	0.152 (2)	0.1049 (18)	0.1022 (17)	−0.0047 (16)	0.0797 (17)	−0.0060 (14)
C7	0.0781 (19)	0.0425 (14)	0.0730 (19)	0.0208 (13)	0.0367 (16)	0.0161 (13)
C14	0.082 (2)	0.0418 (15)	0.0623 (18)	0.0163 (14)	0.0211 (15)	0.0068 (13)
C3	0.0672 (18)	0.071 (2)	0.0613 (18)	0.0240 (15)	0.0219 (15)	−0.0085 (15)
C8	0.109 (3)	0.0563 (18)	0.085 (2)	0.0361 (18)	0.057 (2)	0.0315 (16)
C16	0.091 (2)	0.0459 (16)	0.0621 (18)	0.0197 (15)	0.0182 (16)	−0.0030 (13)
C19	0.094 (3)	0.067 (2)	0.062 (2)	0.0193 (19)	0.0233 (19)	−0.0047 (16)
C9	0.196 (5)	0.104 (3)	0.111 (3)	0.073 (3)	0.105 (4)	0.051 (3)
F2	0.118 (2)	0.248 (4)	0.0599 (14)	−0.032 (2)	0.0136 (14)	0.0125 (18)
F1	0.372 (6)	0.176 (3)	0.126 (2)	0.180 (4)	0.148 (3)	0.048 (2)
O1	0.1138 (18)	0.0424 (11)	0.0871 (15)	0.0259 (11)	0.0525 (14)	0.0177 (10)

Cl1—C1	1.745 (3)	C18—C17	1.377 (4)
O3—C6	1.364 (3)	C18—C16	1.382 (4)
O3—C7	1.416 (3)	C18—C19	1.494 (4)
O2—C10	1.310 (3)	C5—C3	1.366 (4)
O2—H24	0.8200	C5—H5	0.9300
C13—C14	1.384 (4)	C17—H17	0.9300
C13—C15	1.393 (4)	C1—C3	1.372 (5)
C13—C12	1.491 (4)	F3—C19	1.312 (4)
C12—O1	1.265 (3)	C7—C8	1.452 (4)
C12—C11	1.409 (4)	C7—H7A	0.9700
C4—C2	1.390 (4)	C7—H7B	0.9700
C4—C6	1.408 (4)	C14—C16	1.381 (4)
C4—C10	1.484 (4)	C14—H14	0.9300
C2—C1	1.371 (4)	C3—H3	0.9300
C2—H2	0.9300	C8—C9	1.161 (5)
C6—C5	1.388 (4)	C16—H16	0.9300
C10—C11	1.373 (4)	C19—F1	1.283 (4)
C11—H11	0.9300	C19—F2	1.299 (4)
C15—C17	1.372 (4)	C9—H9	0.9300
C15—H15	0.9300
C6—O3—C7	119.4 (2)	C6—C5—H5	119.7
C10—O2—H24	109.5	C15—C17—C18	119.8 (3)
C14—C13—C15	117.9 (3)	C15—C17—H17	120.1
C14—C13—C12	119.7 (3)	C18—C17—H17	120.1
C15—C13—C12	122.4 (2)	C2—C1—C3	120.8 (3)
O1—C12—C11	121.7 (3)	C2—C1—Cl1	119.7 (3)
O1—C12—C13	118.0 (2)	C3—C1—Cl1	119.5 (2)
C11—C12—C13	120.2 (2)	O3—C7—C8	107.8 (2)
C2—C4—C6	117.9 (2)	O3—C7—H7A	110.1
C2—C4—C10	117.5 (2)	C8—C7—H7A	110.1
C6—C4—C10	124.6 (2)	O3—C7—H7B	110.1
C1—C2—C4	120.9 (3)	C8—C7—H7B	110.1
C1—C2—H2	119.6	H7A—C7—H7B	108.5
C4—C2—H2	119.6	C16—C14—C13	121.0 (3)
O3—C6—C5	122.6 (2)	C16—C14—H14	119.5
O3—C6—C4	117.4 (2)	C13—C14—H14	119.5
C5—C6—C4	120.0 (3)	C5—C3—C1	119.8 (3)
O2—C10—C11	120.1 (2)	C5—C3—H3	120.1
O2—C10—C4	114.1 (2)	C1—C3—H3	120.1
C11—C10—C4	125.9 (2)	C9—C8—C7	179.0 (4)
C10—C11—C12	122.4 (2)	C14—C16—C18	119.9 (3)
C10—C11—H11	118.8	C14—C16—H16	120.1
C12—C11—H11	118.8	C18—C16—H16	120.1
C17—C15—C13	121.4 (3)	F1—C19—F2	106.7 (4)
C17—C15—H15	119.3	F1—C19—F3	105.4 (4)
C13—C15—H15	119.3	F2—C19—F3	103.3 (3)
C17—C18—C16	120.0 (3)	F1—C19—C18	113.8 (3)
C17—C18—C19	120.2 (3)	F2—C19—C18	111.9 (3)
C16—C18—C19	119.8 (3)	F3—C19—C18	114.9 (3)
C3—C5—C6	120.6 (3)	C8—C9—H9	180.0
C3—C5—H5	119.7
C14—C13—C12—O1	10.5 (4)	C4—C6—C5—C3	−0.2 (4)
C15—C13—C12—O1	−170.5 (3)	C13—C15—C17—C18	−0.4 (5)
C14—C13—C12—C11	−167.0 (3)	C16—C18—C17—C15	−0.2 (4)
C15—C13—C12—C11	12.0 (4)	C19—C18—C17—C15	178.4 (3)
C6—C4—C2—C1	−0.9 (4)	C4—C2—C1—C3	0.3 (4)
C10—C4—C2—C1	178.5 (2)	C4—C2—C1—Cl1	−179.5 (2)
C7—O3—C6—C5	−1.2 (4)	C6—O3—C7—C8	−178.7 (3)
C7—O3—C6—C4	179.3 (2)	C15—C13—C14—C16	−0.6 (4)
C2—C4—C6—O3	−179.7 (2)	C12—C13—C14—C16	178.4 (3)
C10—C4—C6—O3	1.0 (4)	C6—C5—C3—C1	−0.4 (5)
C2—C4—C6—C5	0.8 (4)	C2—C1—C3—C5	0.4 (5)
C10—C4—C6—C5	−178.5 (3)	Cl1—C1—C3—C5	−179.9 (2)
C2—C4—C10—O2	2.7 (4)	O3—C7—C8—C9	−158 (26)
C6—C4—C10—O2	−178.0 (2)	C13—C14—C16—C18	0.1 (5)
C2—C4—C10—C11	−177.9 (3)	C17—C18—C16—C14	0.3 (5)
C6—C4—C10—C11	1.3 (4)	C19—C18—C16—C14	−178.2 (3)
O2—C10—C11—C12	1.0 (4)	C17—C18—C19—F1	130.3 (4)
C4—C10—C11—C12	−178.2 (2)	C16—C18—C19—F1	−51.1 (5)
O1—C12—C11—C10	−2.2 (4)	C17—C18—C19—F2	−108.6 (4)
C13—C12—C11—C10	175.2 (2)	C16—C18—C19—F2	69.9 (4)
C14—C13—C15—C17	0.7 (4)	C17—C18—C19—F3	8.7 (5)
C12—C13—C15—C17	−178.3 (3)	C16—C18—C19—F3	−172.7 (3)
O3—C6—C5—C3	−179.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H24···O1	0.82	1.79	2.529 (3)	149
C11—H11···O3	0.93	2.09	2.747 (3)	126
C7—H7B···O1i	0.97	2.62	3.476 (4)	147

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O2H24O1	0.82	1.79	2.529(3)	149
C11H11O3	0.93	2.09	2.747(3)	126
C7H7BO1i	0.97	2.62	3.476(4)	147

Symmetry code: (i) .