(Z)-6-[(5-Chloro-2-hydroxy-phenyl)-aminomethyl-ene]-2-ethoxy-cyclo-hexa-2,4-dienone.

The title compound, C(15)H(14)ClNO(3), exists as the keto-amine form in the crystal and two intra-molecular N-H⋯O hydrogen bonds are observed. The aromatic rings are oriented at a dihedral angle of 5.85 (8)°. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into chains. A π-π contact between the benzene rings [centroid-centroid distance = 3.6623 (10) Å] further stabilizes the structure.

Related literature

For general background, see: Büyükgüngör et al. (2007 ▶); Ersanlı et al. (2003 ▶); Tanak et al. (2008 ▶) For related structures, see: Özek et al. (2007 ▶, 2008 ▶).

Experimental

Crystal data

C15H14ClNO3

M = 291.72

Monoclinic,

a = 15.4313 (7) Å

b = 7.1710 (2) Å

c = 12.6071 (6) Å

β = 111.168 (4)°

V = 1300.94 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 296 K

0.52 × 0.29 × 0.09 mm

Data collection

STOE IPDS II diffractometer

Absorption correction: integration X-RED32 (Stoe & Cie, 2002 ▶) T min = 0.616, T max = 0.927

15989 measured reflections

2680 independent reflections

2084 reflections with I > 2σ(I)

R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.099

S = 1.05

2680 reflections

237 parameters

All H-atom parameters refined

Δρmax = 0.15 e Å−3

Δρmin = −0.25 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031298/bt5027sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031298/bt5027Isup2.hkl

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

C15H14ClNO3	F(000) = 608
Mr = 291.72	Dx = 1.489 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15989 reflections
a = 15.4313 (7) Å	θ = 2.8–26.5°
b = 7.1710 (2) Å	µ = 0.30 mm−1
c = 12.6071 (6) Å	T = 296 K
β = 111.168 (4)°	Prism, red
V = 1300.94 (10) Å3	0.52 × 0.29 × 0.09 mm
Z = 4

STOE IPDS II diffractometer	2680 independent reflections
Radiation source: fine-focus sealed tube	2084 reflections with I > 2σ(I)
plane graphite	Rint = 0.060
Detector resolution: 6.67 pixels mm-1	θmax = 26.5°, θmin = 2.8°
ω scans	h = −19→19
Absorption correction: integration X-RED32 (Stoe & Cie, 2002)	k = −8→8
Tmin = 0.616, Tmax = 0.927	l = −15→15
15989 measured reflections

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) = 0.099	All H-atom parameters refined
S = 1.05	w = 1/[σ2(Fo2) + (0.0546P)2 + 0.0402P] where P = (Fo2 + 2Fc2)/3
2680 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. 314 frames, detector distance = 100 mm

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
C1	0.42045 (11)	0.1210 (2)	0.12588 (13)	0.0348 (3)
C2	0.35762 (11)	0.0951 (2)	0.18490 (13)	0.0347 (3)
C3	0.25975 (11)	0.0968 (2)	0.11617 (14)	0.0354 (4)
C4	0.23136 (12)	0.1153 (2)	0.00038 (14)	0.0405 (4)
C5	0.29497 (13)	0.1391 (3)	−0.05529 (15)	0.0420 (4)
C6	0.38735 (12)	0.1431 (2)	0.00582 (14)	0.0397 (4)
C7	0.10537 (12)	0.1023 (3)	0.11398 (16)	0.0429 (4)
C8	0.05590 (13)	0.1030 (4)	0.19698 (19)	0.0515 (5)
C9	0.51704 (11)	0.1302 (2)	0.18651 (15)	0.0372 (4)
C10	0.65028 (11)	0.1159 (2)	0.36438 (14)	0.0349 (3)
C11	0.67292 (11)	0.1056 (2)	0.48215 (14)	0.0366 (4)
C12	0.76552 (12)	0.0967 (3)	0.55291 (16)	0.0435 (4)
C13	0.83466 (12)	0.0983 (3)	0.50765 (16)	0.0446 (4)
C14	0.81081 (11)	0.1101 (2)	0.39143 (16)	0.0398 (4)
C15	0.71950 (12)	0.1205 (2)	0.31875 (15)	0.0385 (4)
N1	0.55488 (9)	0.1157 (2)	0.29736 (12)	0.0375 (3)
O1	0.38649 (8)	0.07391 (19)	0.29284 (10)	0.0458 (3)
O2	0.20269 (8)	0.08261 (18)	0.17686 (10)	0.0432 (3)
O3	0.60157 (9)	0.10408 (19)	0.52038 (11)	0.0462 (3)
Cl1	0.89826 (3)	0.10870 (7)	0.33413 (5)	0.05476 (17)
H1	0.5154 (16)	0.095 (3)	0.3294 (19)	0.057 (6)*
H3	0.6156 (16)	0.048 (3)	0.584 (2)	0.058 (6)*
H4	0.1662 (17)	0.112 (3)	−0.044 (2)	0.067 (7)*
H5	0.2700 (13)	0.157 (3)	−0.1342 (18)	0.048 (5)*
H6	0.4309 (14)	0.169 (3)	−0.0299 (16)	0.047 (5)*
H7A	0.0925 (14)	0.221 (3)	0.0713 (18)	0.055 (6)*
H7B	0.0851 (14)	−0.005 (3)	0.0600 (18)	0.049 (5)*
H8A	0.0771 (17)	0.197 (3)	0.250 (2)	0.067 (7)*
H8B	0.0646 (15)	−0.015 (4)	0.2363 (19)	0.063 (6)*
H8C	−0.0076 (18)	0.120 (3)	0.157 (2)	0.068 (7)*
H9	0.5538 (13)	0.150 (2)	0.1399 (16)	0.041 (5)*
H12	0.7798 (15)	0.087 (3)	0.633 (2)	0.055 (6)*
H13	0.8974 (15)	0.090 (3)	0.5585 (18)	0.053 (6)*
H15	0.7051 (13)	0.124 (3)	0.2410 (18)	0.046 (5)*

	U11	U22	U33	U12	U13	U23
C1	0.0326 (8)	0.0412 (8)	0.0316 (8)	0.0001 (7)	0.0127 (6)	−0.0005 (7)
C2	0.0332 (8)	0.0416 (8)	0.0302 (8)	0.0009 (7)	0.0124 (6)	0.0021 (6)
C3	0.0329 (8)	0.0404 (8)	0.0331 (8)	−0.0007 (7)	0.0122 (6)	−0.0005 (7)
C4	0.0356 (8)	0.0490 (9)	0.0333 (8)	0.0003 (7)	0.0081 (7)	−0.0003 (7)
C5	0.0454 (10)	0.0520 (11)	0.0264 (8)	0.0044 (8)	0.0103 (7)	0.0021 (7)
C6	0.0425 (9)	0.0470 (10)	0.0344 (9)	0.0034 (7)	0.0197 (7)	0.0042 (7)
C7	0.0294 (8)	0.0547 (11)	0.0421 (9)	0.0028 (8)	0.0099 (7)	0.0023 (9)
C8	0.0334 (9)	0.0712 (14)	0.0510 (11)	0.0059 (9)	0.0167 (9)	0.0038 (11)
C9	0.0349 (8)	0.0439 (9)	0.0368 (8)	−0.0001 (7)	0.0178 (7)	0.0027 (7)
C10	0.0298 (7)	0.0389 (8)	0.0367 (9)	−0.0004 (6)	0.0129 (6)	0.0021 (7)
C11	0.0352 (8)	0.0407 (8)	0.0373 (8)	0.0004 (7)	0.0172 (7)	0.0021 (7)
C12	0.0382 (9)	0.0533 (10)	0.0365 (9)	0.0016 (8)	0.0102 (7)	0.0024 (8)
C13	0.0312 (8)	0.0510 (10)	0.0475 (10)	0.0006 (7)	0.0091 (7)	0.0016 (8)
C14	0.0313 (8)	0.0409 (9)	0.0511 (10)	−0.0009 (7)	0.0197 (7)	0.0017 (8)
C15	0.0361 (8)	0.0447 (9)	0.0383 (9)	0.0008 (7)	0.0178 (7)	0.0007 (7)
N1	0.0295 (7)	0.0513 (8)	0.0334 (7)	−0.0013 (6)	0.0136 (6)	0.0017 (6)
O1	0.0332 (6)	0.0767 (9)	0.0287 (6)	−0.0018 (6)	0.0125 (5)	0.0055 (6)
O2	0.0277 (6)	0.0683 (8)	0.0333 (6)	−0.0003 (5)	0.0107 (5)	0.0035 (5)
O3	0.0403 (7)	0.0646 (8)	0.0403 (7)	0.0069 (6)	0.0225 (6)	0.0103 (6)
Cl1	0.0386 (2)	0.0643 (3)	0.0721 (3)	0.0028 (2)	0.0328 (2)	0.0067 (2)

C1—C9	1.410 (2)	C8—H8C	0.93 (3)
C1—C6	1.421 (2)	C9—N1	1.310 (2)
C1—C2	1.432 (2)	C9—H9	0.96 (2)
C2—O1	1.279 (2)	C10—C15	1.384 (2)
C2—C3	1.445 (2)	C10—C11	1.399 (2)
C3—O2	1.363 (2)	C10—N1	1.408 (2)
C3—C4	1.371 (2)	C11—O3	1.3519 (19)
C4—C5	1.408 (3)	C11—C12	1.386 (2)
C4—H4	0.96 (2)	C12—C13	1.380 (3)
C5—C6	1.354 (2)	C12—H12	0.95 (2)
C5—H5	0.94 (2)	C13—C14	1.378 (3)
C6—H6	0.95 (2)	C13—H13	0.95 (2)
C7—O2	1.430 (2)	C14—C15	1.378 (2)
C7—C8	1.502 (3)	C14—Cl1	1.7456 (17)
C7—H7A	0.99 (2)	C15—H15	0.92 (2)
C7—H7B	1.00 (2)	N1—H1	0.86 (2)
C8—H8A	0.92 (2)	O3—H3	0.85 (2)
C8—H8B	0.97 (2)
C9—C1—C6	118.39 (15)	H8A—C8—H8C	109 (2)
C9—C1—C2	120.41 (15)	H8B—C8—H8C	108.4 (19)
C6—C1—C2	121.18 (14)	N1—C9—C1	123.47 (15)
O1—C2—C1	121.83 (14)	N1—C9—H9	121.9 (11)
O1—C2—C3	121.77 (14)	C1—C9—H9	114.6 (11)
C1—C2—C3	116.40 (14)	C15—C10—C11	120.52 (15)
O2—C3—C4	125.61 (15)	C15—C10—N1	123.16 (15)
O2—C3—C2	114.20 (14)	C11—C10—N1	116.29 (14)
C4—C3—C2	120.18 (15)	O3—C11—C12	123.59 (16)
C3—C4—C5	122.02 (16)	O3—C11—C10	117.09 (15)
C3—C4—H4	118.9 (14)	C12—C11—C10	119.32 (15)
C5—C4—H4	119.0 (14)	C13—C12—C11	120.32 (17)
C6—C5—C4	119.94 (16)	C13—C12—H12	121.3 (13)
C6—C5—H5	123.1 (12)	C11—C12—H12	118.4 (13)
C4—C5—H5	116.9 (12)	C14—C13—C12	119.38 (16)
C5—C6—C1	120.23 (16)	C14—C13—H13	122.5 (13)
C5—C6—H6	120.8 (12)	C12—C13—H13	118.1 (13)
C1—C6—H6	118.8 (12)	C15—C14—C13	121.78 (16)
O2—C7—C8	108.09 (15)	C15—C14—Cl1	118.87 (14)
O2—C7—H7A	110.6 (12)	C13—C14—Cl1	119.34 (13)
C8—C7—H7A	108.8 (12)	C14—C15—C10	118.66 (16)
O2—C7—H7B	108.1 (12)	C14—C15—H15	120.2 (12)
C8—C7—H7B	111.4 (12)	C10—C15—H15	121.0 (12)
H7A—C7—H7B	109.8 (17)	C9—N1—C10	127.35 (15)
C7—C8—H8A	111.7 (15)	C9—N1—H1	113.4 (15)
C7—C8—H8B	110.1 (14)	C10—N1—H1	119.0 (15)
H8A—C8—H8B	109 (2)	C3—O2—C7	116.33 (13)
C7—C8—H8C	109.0 (15)	C11—O3—H3	112.0 (16)
C9—C1—C2—O1	−2.2 (3)	C15—C10—C11—C12	−1.1 (3)
C6—C1—C2—O1	179.60 (16)	N1—C10—C11—C12	177.13 (16)
C9—C1—C2—C3	176.96 (15)	O3—C11—C12—C13	179.80 (17)
C6—C1—C2—C3	−1.3 (2)	C10—C11—C12—C13	0.1 (3)
O1—C2—C3—O2	2.8 (2)	C11—C12—C13—C14	0.5 (3)
C1—C2—C3—O2	−176.34 (14)	C12—C13—C14—C15	0.0 (3)
O1—C2—C3—C4	−178.42 (16)	C12—C13—C14—Cl1	−179.07 (14)
C1—C2—C3—C4	2.5 (2)	C13—C14—C15—C10	−1.0 (3)
O2—C3—C4—C5	176.54 (16)	Cl1—C14—C15—C10	178.08 (13)
C2—C3—C4—C5	−2.1 (3)	C11—C10—C15—C14	1.5 (3)
C3—C4—C5—C6	0.4 (3)	N1—C10—C15—C14	−176.58 (16)
C4—C5—C6—C1	0.8 (3)	C1—C9—N1—C10	177.28 (17)
C9—C1—C6—C5	−178.59 (17)	C15—C10—N1—C9	−4.2 (3)
C2—C1—C6—C5	−0.3 (3)	C11—C10—N1—C9	177.63 (17)
C6—C1—C9—N1	178.49 (16)	C4—C3—O2—C7	−4.7 (2)
C2—C1—C9—N1	0.2 (3)	C2—C3—O2—C7	174.00 (15)
C15—C10—C11—O3	179.17 (15)	C8—C7—O2—C3	−174.00 (16)
N1—C10—C11—O3	−2.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86 (2)	1.88 (2)	2.5957 (17)	140 (2)
N1—H1···O3	0.86 (2)	2.29 (2)	2.640 (2)	104.3 (17)
O3—H3···O1i	0.85 (2)	1.79 (2)	2.6258 (17)	165 (2)
C9—H9···O3ii	0.96 (2)	2.594 (19)	3.419 (2)	143.8 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86 (2)	1.88 (2)	2.5957 (17)	140 (2)
N1—H1⋯O3	0.86 (2)	2.29 (2)	2.640 (2)	104.3 (17)
O3—H3⋯O1i	0.85 (2)	1.79 (2)	2.6258 (17)	165 (2)
C9—H9⋯O3ii	0.96 (2)	2.594 (19)	3.419 (2)	143.8 (14)

Symmetry codes: (i) ; (ii) .