(Z)-3-Hydr­oxy-6-[(2-methoxy­phenyl­amino)methyl­ene]cyclo­hexa-2,4-dienone

The title compound, C₁₄H₁₃N₁O₃, adopts the keto–amine tautomeric form, with an intra­molecular N—H...O resonance-assisted hydrogen bond. The two benzene rings are nearly coplanar [dihedral angle = 14.3 (2)°]. The mol­ecules are linked by inter­molecular O—H...O hydrogen bonds and C—H... π inter­actions between meth­yl groups and benzene rings.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.059
• wR factor = 0.192
• Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O3
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.00
           From the CIF: _reflns_number_total               1788
           Count of symmetry unique reflns         1788
           Completeness (_total/calc)            100.00%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1998).

(Z)-3-hydroxy-6-[(2-methoxyphenylamino)methylene]cyclohexa-2,4-dienone

Crystal data

C14H13NO3	Dx = 1.256 Mg m^−3
Mr = 243.25	Melting point = 423–4425 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac2ab	Cell parameters from 21062 reflections
a = 8.3391 (7) Å	θ = 2.3–26.0°
b = 11.1748 (15) Å	µ = 0.09 mm^−1
c = 13.8056 (19) Å	T = 296 K
V = 1286.5 (3) Å^3	Prism, yellow
Z = 4	0.35 × 0.31 × 0.27 mm
F(000) = 512

Data collection

Stoe IPDS-2 diffractometer	1788 independent reflections
Radiation source: fine-focus sealed tube	1007 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.077
Detector resolution: 6.67 pixels mm^-1	θmax = 28.0°, θmin = 2.3°
ω scans	h = −11→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −14→14
Tmin = 0.972, Tmax = 0.981	l = −18→18
21062 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.192	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1182P)^2] where P = (Fo^2 + 2Fc^2)/3
1788 reflections	(Δ/σ)max < 0.001
152 parameters	Δρmax = 0.24 e Å^−3
1 restraint	Δρmin = −0.24 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5725 (5)	0.5839 (3)	0.2050 (3)	0.0568 (9)
C2	0.5554 (4)	0.6689 (3)	0.1265 (2)	0.0526 (8)
C3	0.6756 (4)	0.6696 (4)	0.0551 (3)	0.0536 (9)
H3	0.6681	0.7233	0.0038	0.064*
C4	0.8044 (5)	0.5924 (3)	0.0594 (3)	0.0579 (10)
C5	0.8182 (5)	0.5089 (4)	0.1356 (3)	0.0708 (12)
H5	0.9039	0.4557	0.1373	0.085*
C6	0.7064 (6)	0.5069 (4)	0.2058 (3)	0.0711 (11)
H6	0.7177	0.4529	0.2565	0.085*
C7	0.4583 (5)	0.5769 (4)	0.2782 (3)	0.0645 (11)
H7	0.4753	0.5225	0.3281	0.077*
C8	0.2062 (6)	0.6424 (4)	0.3507 (4)	0.0759 (13)
C9	0.0663 (6)	0.7068 (4)	0.3251 (5)	0.0900 (17)
C10	−0.0590 (9)	0.7088 (6)	0.3916 (5)	0.111
H10	−0.1543	0.7483	0.3774	0.133*
C11	−0.0388 (10)	0.6513 (6)	0.4787 (6)	0.128
H11	−0.1228	0.6537	0.5229	0.154*
C12	0.0984 (10)	0.5900 (6)	0.5047 (5)	0.125
H12	0.1068	0.5528	0.5647	0.150*
C13	0.2220 (8)	0.5859 (5)	0.4393 (4)	0.0951 (17)
H13	0.3160	0.5452	0.4544	0.114*
C14	−0.0660 (7)	0.8279 (7)	0.2074 (4)	0.111
H14A	−0.0998	0.8796	0.2591	0.167*
H14B	−0.1520	0.7747	0.1905	0.167*
H14C	−0.0372	0.8752	0.1521	0.167*
N1	0.3283 (4)	0.6424 (3)	0.2809 (3)	0.0655 (9)
H1	0.3162	0.6920	0.2338	0.079*
O1	0.4332 (3)	0.7389 (3)	0.12324 (19)	0.0692 (8)
O2	0.9220 (4)	0.5901 (3)	−0.0061 (2)	0.0730 (9)
O3	0.0687 (4)	0.7600 (3)	0.2380 (3)	0.084
H2	0.926 (9)	0.655 (4)	−0.046 (4)	0.126*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.063 (2)	0.055 (2)	0.052 (2)	−0.006 (2)	−0.003 (2)	0.0115 (17)
C2	0.0533 (19)	0.0572 (19)	0.0474 (17)	−0.0064 (19)	−0.0089 (17)	0.0075 (17)
C3	0.060 (2)	0.0507 (18)	0.0495 (17)	−0.0023 (19)	−0.0058 (17)	0.0130 (17)
C4	0.064 (2)	0.0514 (19)	0.058 (2)	−0.002 (2)	−0.001 (2)	0.0086 (18)
C5	0.075 (3)	0.058 (2)	0.080 (3)	0.017 (2)	0.004 (3)	0.016 (2)
C6	0.081 (3)	0.066 (2)	0.066 (3)	0.015 (3)	−0.001 (2)	0.020 (2)
C7	0.073 (3)	0.067 (2)	0.054 (2)	−0.010 (2)	−0.002 (2)	0.0105 (19)
C8	0.081 (3)	0.068 (3)	0.078 (3)	−0.023 (3)	0.023 (3)	−0.011 (2)
C9	0.074 (3)	0.070 (3)	0.126 (4)	−0.028 (3)	0.030 (3)	−0.044 (3)
C10	0.120	0.104	0.107	−0.028 (4)	0.037 (4)	−0.028 (3)
C11	0.135	0.119	0.131	−0.053 (4)	0.077 (3)	−0.038 (4)
C12	0.135	0.119	0.121	−0.036 (4)	0.060 (4)	0.002 (4)
C13	0.120 (4)	0.080 (3)	0.086 (4)	−0.028 (3)	0.035 (3)	0.004 (3)
C14	0.089	0.136	0.109	0.022 (4)	−0.038 (3)	−0.043 (4)
N1	0.072 (2)	0.066 (2)	0.0584 (19)	−0.010 (2)	0.0062 (17)	0.0059 (16)
O1	0.0604 (16)	0.0841 (19)	0.0633 (15)	0.0128 (16)	0.0004 (14)	0.0220 (15)
O2	0.0750 (18)	0.0642 (17)	0.080 (2)	0.0099 (16)	0.0185 (18)	0.0147 (16)
O3	0.076	0.088	0.086	0.0036 (19)	−0.0046 (19)	−0.0070 (19)

Geometric parameters (Å, º)

C1—C7	1.391 (6)	C8—C9	1.416 (7)
C1—C6	1.410 (6)	C9—O3	1.342 (7)
C1—C2	1.448 (5)	C9—C10	1.390 (8)
C2—O1	1.286 (5)	C10—C11	1.374 (10)
C2—C3	1.406 (5)	C10—H10	0.9300
C3—C4	1.379 (5)	C11—C12	1.381 (11)
C3—H3	0.9300	C11—H11	0.9300
C4—O2	1.333 (5)	C12—C13	1.371 (8)
C4—C5	1.411 (6)	C12—H12	0.9300
C5—C6	1.345 (6)	C13—H13	0.9300
C5—H5	0.9300	C14—O3	1.419 (6)
C6—H6	0.9300	C14—H14A	0.9600
C7—N1	1.309 (5)	C14—H14B	0.9600
C7—H7	0.9300	C14—H14C	0.9600
C8—C13	1.383 (8)	N1—H1	0.8600
C8—N1	1.401 (5)	O2—H2	0.91 (4)
C7—C1—C6	120.1 (4)	O3—C9—C8	115.9 (4)
C7—C1—C2	120.9 (4)	C10—C9—C8	117.6 (6)
C6—C1—C2	118.9 (3)	C11—C10—C9	118.5 (7)
O1—C2—C3	122.5 (3)	C11—C10—H10	120.7
O1—C2—C1	120.2 (3)	C9—C10—H10	120.7
C3—C2—C1	117.3 (3)	C10—C11—C12	124.1 (6)
C4—C3—C2	121.4 (3)	C10—C11—H11	117.9
C4—C3—H3	119.3	C12—C11—H11	117.9
C2—C3—H3	119.3	C13—C12—C11	117.9 (7)
O2—C4—C3	123.7 (3)	C13—C12—H12	121.0
O2—C4—C5	115.6 (4)	C11—C12—H12	121.0
C3—C4—C5	120.6 (4)	C12—C13—C8	119.8 (7)
C6—C5—C4	119.4 (4)	C12—C13—H13	120.1
C6—C5—H5	120.3	C8—C13—H13	120.1
C4—C5—H5	120.3	O3—C14—H14A	109.5
C5—C6—C1	122.3 (4)	O3—C14—H14B	109.5
C5—C6—H6	118.9	H14A—C14—H14B	109.5
C1—C6—H6	118.9	O3—C14—H14C	109.5
N1—C7—C1	123.8 (4)	H14A—C14—H14C	109.5
N1—C7—H7	118.1	H14B—C14—H14C	109.5
C1—C7—H7	118.1	C7—N1—C8	128.4 (4)
C13—C8—N1	122.6 (5)	C7—N1—H1	115.8
C13—C8—C9	122.0 (5)	C8—N1—H1	115.8
N1—C8—C9	115.3 (4)	C4—O2—H2	115 (4)
O3—C9—C10	126.5 (6)	C9—O3—C14	119.5 (4)
C7—C1—C2—O1	−0.4 (6)	N1—C8—C9—O3	−0.4 (6)
C6—C1—C2—O1	178.9 (4)	C13—C8—C9—C10	−1.8 (7)
C7—C1—C2—C3	−179.6 (4)	N1—C8—C9—C10	179.6 (4)
C6—C1—C2—C3	−0.2 (5)	O3—C9—C10—C11	−178.5 (5)
O1—C2—C3—C4	−179.0 (4)	C8—C9—C10—C11	1.6 (8)
C1—C2—C3—C4	0.2 (5)	C9—C10—C11—C12	−0.5 (10)
C2—C3—C4—O2	−179.5 (4)	C10—C11—C12—C13	−0.4 (11)
C2—C3—C4—C5	0.8 (6)	C11—C12—C13—C8	0.1 (9)
O2—C4—C5—C6	178.6 (4)	N1—C8—C13—C12	179.4 (5)
C3—C4—C5—C6	−1.6 (6)	C9—C8—C13—C12	1.0 (8)
C4—C5—C6—C1	1.5 (7)	C1—C7—N1—C8	179.9 (4)
C7—C1—C6—C5	178.7 (4)	C13—C8—N1—C7	12.8 (7)
C2—C1—C6—C5	−0.6 (7)	C9—C8—N1—C7	−168.6 (4)
C6—C1—C7—N1	−177.7 (4)	C10—C9—O3—C14	1.0 (7)
C2—C1—C7—N1	1.6 (6)	C8—C9—O3—C14	−179.1 (4)
C13—C8—C9—O3	178.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.89	2.582 (4)	137
O2—H2···O1^i	0.91 (4)	1.60 (4)	2.506 (4)	175 (6)
C14—H14B···Cg1^ii	0.96	2.60	3.529 (7)	162

Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) x+1, y, z.