(Z)-6-[(5-Chloro-2-hydroxy-anilino)-methyl-ene]-4-methoxy-cyclo-hexa-2,4-dienone 0.25-hydrate.

The title compound, C(14)H(12)ClNO(3)·0.25H(2)O, exists in the keto-amine form, and the aromatic rings are oriented at a dihedral angle of 7.24 (7)°. Bifurcated intra-molecular N-H⋯(O,O) hydrogen bonds result in the formation of planar six- and five-membered rings. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into chains. π-π contacts between benzene rings [centroid-centroid distance = 3.5065 (9) Å] may further stabilize the structure. There also exists a weak C-H⋯π inter-action.

Related literature

For general background, see: Büyükgüngör et al. (2007 ▶); Hökelek et al. (2004 ▶); Odabaşoğlu et al. (2004 ▶). For related structures, see: Özek et al. (2007 ▶, 2008 ▶); Ersanlı et al. (2003 ▶).

Experimental

Crystal data

C14H12ClNO3·0.25H2O

M = 279.95

Monoclinic,

a = 21.3670 (11) Å

b = 6.7600 (3) Å

c = 17.7404 (9) Å

β = 103.841 (4)°

V = 2488.0 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.31 mm−1

T = 100 K

0.68 × 0.54 × 0.41 mm

Data collection

Stoe IPDS-II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.970, T max = 0.970

6976 measured reflections

2588 independent reflections

2352 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.086

S = 1.09

2588 reflections

186 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.31 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-RED32 (Stoe & Cie, 2002 ▶); data reduction: X-RED32; 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901410X/hk2658sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901410X/hk2658Isup2.hkl

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

C14H12ClNO3·0.25H2O	F(000) = 1162
Mr = 279.95	Dx = 1.495 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6976 reflections
a = 21.3670 (11) Å	θ = 2.0–28.0°
b = 6.7600 (3) Å	µ = 0.31 mm−1
c = 17.7404 (9) Å	T = 100 K
β = 103.841 (4)°	Prism, red
V = 2488.0 (2) Å3	0.68 × 0.54 × 0.41 mm
Z = 8

Stoe IPDS-II diffractometer	2588 independent reflections
Radiation source: fine-focus sealed tube	2352 reflections with I > 2σ(I)
plane graphite	Rint = 0.022
Detector resolution: 6.67 pixels mm-1	θmax = 26.5°, θmin = 2.0°
ω scans	h = −25→26
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −8→7
Tmin = 0.970, Tmax = 0.970	l = −22→22
6976 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0376P)2 + 3.3917P] where P = (Fo2 + 2Fc2)/3
2588 reflections	(Δ/σ)max = 0.001
186 parameters	Δρmax = 0.28 e Å−3
2 restraints	Δρmin = −0.31 e Å−3

Experimental. 141 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	Occ. (<1)
C1	0.64391 (7)	0.8209 (2)	0.49336 (8)	0.0163 (3)
C2	0.63352 (7)	0.6614 (2)	0.43854 (8)	0.0171 (3)
C3	0.58193 (7)	0.6836 (2)	0.37118 (9)	0.0191 (3)
H3	0.5736	0.5834	0.3342	0.023*
C4	0.54480 (7)	0.8493 (2)	0.36036 (8)	0.0189 (3)
H4	0.5112	0.8593	0.3162	0.023*
C5	0.55578 (7)	1.0069 (2)	0.41439 (8)	0.0175 (3)
C6	0.60491 (7)	0.9945 (2)	0.47962 (8)	0.0170 (3)
H6	0.6129	1.0986	0.5149	0.020*
C7	0.51514 (8)	1.3060 (2)	0.45380 (9)	0.0211 (3)
H7A	0.5063	1.2434	0.4987	0.032*
H7B	0.4832	1.4055	0.4349	0.032*
H7C	0.5570	1.3663	0.4675	0.032*
C8	0.69160 (7)	0.8057 (2)	0.56359 (8)	0.0164 (3)
H8	0.6987	0.9125	0.5976	0.020*
C9	0.77299 (7)	0.6029 (2)	0.65047 (8)	0.0158 (3)
C10	0.79878 (7)	0.4110 (2)	0.65524 (9)	0.0181 (3)
C11	0.84717 (7)	0.3589 (2)	0.71999 (9)	0.0201 (3)
H11	0.8645	0.2321	0.7238	0.024*
C12	0.86950 (7)	0.4950 (2)	0.77875 (8)	0.0190 (3)
H12	0.9020	0.4604	0.8218	0.023*
C13	0.84290 (7)	0.6831 (2)	0.77270 (8)	0.0175 (3)
C14	0.79444 (7)	0.7395 (2)	0.70949 (8)	0.0172 (3)
H14	0.7767	0.8657	0.7066	0.021*
Cl1	0.873014 (18)	0.85790 (6)	0.84450 (2)	0.02270 (12)
N1	0.72613 (6)	0.64456 (19)	0.58204 (7)	0.0165 (3)
H1	0.7192	0.5522	0.5477	0.020*
O1	0.66836 (5)	0.50302 (16)	0.45048 (6)	0.0219 (3)
O2	0.51359 (5)	1.16195 (17)	0.39490 (6)	0.0229 (3)
O3	0.77355 (5)	0.28754 (18)	0.59629 (7)	0.0236 (3)
H3A	0.7990 (11)	0.196 (3)	0.5898 (15)	0.055 (8)*
O4	0.5000	0.3573 (10)	0.2500	0.0253 (14)	0.25
H4A	0.500 (4)	0.286 (5)	0.2880 (13)	0.03 (2)*	0.25

	U11	U22	U33	U12	U13	U23
C1	0.0144 (7)	0.0192 (7)	0.0150 (6)	−0.0005 (6)	0.0028 (5)	−0.0001 (6)
C2	0.0154 (7)	0.0190 (7)	0.0166 (7)	0.0000 (6)	0.0033 (5)	−0.0010 (6)
C3	0.0184 (7)	0.0226 (8)	0.0155 (7)	−0.0012 (6)	0.0023 (6)	−0.0039 (6)
C4	0.0166 (7)	0.0262 (8)	0.0127 (7)	−0.0004 (6)	0.0012 (5)	0.0000 (6)
C5	0.0158 (7)	0.0202 (7)	0.0167 (7)	0.0021 (6)	0.0043 (5)	0.0017 (6)
C6	0.0173 (7)	0.0187 (7)	0.0147 (6)	0.0001 (6)	0.0037 (5)	−0.0016 (5)
C7	0.0221 (8)	0.0180 (7)	0.0213 (7)	0.0030 (6)	0.0017 (6)	−0.0009 (6)
C8	0.0142 (7)	0.0192 (7)	0.0161 (7)	−0.0004 (6)	0.0045 (5)	−0.0018 (6)
C9	0.0119 (6)	0.0217 (7)	0.0139 (6)	0.0004 (6)	0.0031 (5)	0.0008 (6)
C10	0.0165 (7)	0.0194 (7)	0.0180 (7)	0.0003 (6)	0.0031 (6)	−0.0021 (6)
C11	0.0178 (7)	0.0196 (7)	0.0220 (7)	0.0035 (6)	0.0030 (6)	0.0025 (6)
C12	0.0153 (7)	0.0245 (8)	0.0158 (7)	0.0016 (6)	0.0011 (5)	0.0043 (6)
C13	0.0143 (7)	0.0235 (8)	0.0146 (7)	−0.0019 (6)	0.0035 (5)	−0.0017 (6)
C14	0.0158 (7)	0.0183 (7)	0.0166 (7)	0.0018 (6)	0.0021 (5)	0.0009 (6)
Cl1	0.0219 (2)	0.0258 (2)	0.01674 (19)	0.00025 (14)	−0.00266 (14)	−0.00406 (14)
N1	0.0151 (6)	0.0184 (6)	0.0142 (6)	0.0007 (5)	0.0001 (5)	−0.0018 (5)
O1	0.0205 (5)	0.0206 (6)	0.0221 (5)	0.0040 (4)	0.0002 (4)	−0.0053 (4)
O2	0.0226 (6)	0.0233 (6)	0.0189 (5)	0.0078 (4)	−0.0030 (4)	−0.0015 (4)
O3	0.0206 (6)	0.0228 (6)	0.0238 (6)	0.0049 (5)	−0.0016 (4)	−0.0077 (5)
O4	0.036 (4)	0.021 (3)	0.016 (3)	0.000	−0.001 (3)	0.000

C1—C8	1.412 (2)	C8—H8	0.9300
C1—C6	1.426 (2)	C9—C14	1.389 (2)
C1—C2	1.433 (2)	C9—C10	1.404 (2)
C2—O1	1.2924 (18)	C9—N1	1.4050 (18)
C2—C3	1.427 (2)	C10—O3	1.3459 (18)
C3—C4	1.359 (2)	C10—C11	1.395 (2)
C3—H3	0.9300	C11—C12	1.387 (2)
C4—C5	1.415 (2)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.386 (2)
C5—C6	1.366 (2)	C12—H12	0.9300
C5—O2	1.3720 (18)	C13—C14	1.385 (2)
C6—H6	0.9300	C13—Cl1	1.7438 (15)
C7—O2	1.4229 (19)	C14—H14	0.9300
C7—H7A	0.9600	N1—H1	0.8600
C7—H7B	0.9600	O3—H3A	0.852 (17)
C7—H7C	0.9600	O4—H4A	0.831 (19)
C8—N1	1.3122 (19)
C8—C1—C6	118.69 (13)	N1—C8—H8	119.2
C8—C1—C2	120.36 (14)	C1—C8—H8	119.2
C6—C1—C2	120.91 (13)	C14—C9—C10	120.98 (13)
O1—C2—C3	121.57 (14)	C14—C9—N1	123.82 (13)
O1—C2—C1	121.51 (13)	C10—C9—N1	115.19 (13)
C3—C2—C1	116.90 (14)	O3—C10—C11	124.28 (14)
C4—C3—C2	120.85 (14)	O3—C10—C9	116.60 (13)
C4—C3—H3	119.6	C11—C10—C9	119.10 (14)
C2—C3—H3	119.6	C12—C11—C10	120.35 (14)
C3—C4—C5	121.89 (13)	C12—C11—H11	119.8
C3—C4—H4	119.1	C10—C11—H11	119.8
C5—C4—H4	119.1	C13—C12—C11	119.30 (13)
C6—C5—O2	125.86 (14)	C13—C12—H12	120.3
C6—C5—C4	119.79 (14)	C11—C12—H12	120.3
O2—C5—C4	114.34 (12)	C14—C13—C12	121.88 (14)
C5—C6—C1	119.64 (14)	C14—C13—Cl1	118.58 (12)
C5—C6—H6	120.2	C12—C13—Cl1	119.49 (11)
C1—C6—H6	120.2	C13—C14—C9	118.37 (14)
O2—C7—H7A	109.5	C13—C14—H14	120.8
O2—C7—H7B	109.5	C9—C14—H14	120.8
H7A—C7—H7B	109.5	C8—N1—C9	128.60 (13)
O2—C7—H7C	109.5	C8—N1—H1	115.7
H7A—C7—H7C	109.5	C9—N1—H1	115.7
H7B—C7—H7C	109.5	C5—O2—C7	116.07 (11)
N1—C8—C1	121.66 (14)	C10—O3—H3A	114.0 (18)
C8—C1—C2—O1	−2.1 (2)	C14—C9—C10—C11	−0.7 (2)
C6—C1—C2—O1	−179.69 (14)	N1—C9—C10—C11	177.86 (14)
C8—C1—C2—C3	176.39 (14)	O3—C10—C11—C12	−178.82 (15)
C6—C1—C2—C3	−1.2 (2)	C9—C10—C11—C12	−0.1 (2)
O1—C2—C3—C4	178.48 (14)	C10—C11—C12—C13	0.5 (2)
C1—C2—C3—C4	0.0 (2)	C11—C12—C13—C14	0.0 (2)
C2—C3—C4—C5	0.6 (2)	C11—C12—C13—Cl1	−177.44 (12)
C3—C4—C5—C6	0.0 (2)	C12—C13—C14—C9	−0.9 (2)
C3—C4—C5—O2	−179.47 (14)	Cl1—C13—C14—C9	176.63 (11)
O2—C5—C6—C1	178.19 (14)	C10—C9—C14—C13	1.2 (2)
C4—C5—C6—C1	−1.2 (2)	N1—C9—C14—C13	−177.27 (14)
C8—C1—C6—C5	−175.82 (14)	C1—C8—N1—C9	−176.94 (14)
C2—C1—C6—C5	1.8 (2)	C14—C9—N1—C8	−5.5 (2)
C6—C1—C8—N1	175.38 (14)	C10—C9—N1—C8	175.95 (14)
C2—C1—C8—N1	−2.3 (2)	C6—C5—O2—C7	−10.6 (2)
C14—C9—C10—O3	178.07 (14)	C4—C5—O2—C7	168.79 (13)
N1—C9—C10—O3	−3.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.84	2.5511 (16)	140
N1—H1···O3	0.86	2.19	2.6063 (17)	109
C3—H3···O4	0.93	2.43	3.279 (5)	151
O4—H4A···O2i	0.83 (2)	2.03 (2)	2.842 (3)	166 (6)
O3—H3A···O1ii	0.85 (2)	1.74 (2)	2.5652 (16)	162 (3)
C12—H12···O2iii	0.93	2.56	3.4372 (18)	157
C7—H7A···Cg1iv	0.96	2.83	3.644 (2)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.84	2.5511 (16)	140
N1—H1⋯O3	0.86	2.19	2.6063 (17)	109
C3—H3⋯O4	0.93	2.43	3.279 (5)	151
O4—H4A⋯O2i	0.831 (19)	2.029 (19)	2.842 (3)	166 (6)
O3—H3A⋯O1ii	0.852 (17)	1.743 (18)	2.5652 (16)	162 (3)
C12—H12⋯O2iii	0.93	2.56	3.4372 (18)	157
C7—H7A⋯Cg1iv	0.96	2.83	3.644 (2)	143

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg1 is the centroid of the C1–C6 ring.