The title compound, C
14H
13N
1O
3, 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.
Supporting information
CCDC reference: 283945
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (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
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
top
Crystal data top
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) Å3 | Prism, yellow |
Z = 4 | 0.35 × 0.31 × 0.27 mm |
F(000) = 512 | |
Data collection top
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 top
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.192 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.1182P)2] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) top
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···O1i | 0.91 (4) | 1.60 (4) | 2.506 (4) | 175 (6) |
C14—H14B···Cg1ii | 0.96 | 2.60 | 3.529 (7) | 162 |
Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) x+1, y, z. |