Crystal structure and Hirshfeld surface analysis of a Schiff base: (Z)-6-[(5-chloro-2-meth­oxy­anilino)methyl­idene]-2-hy­droxy­cyclo­hexa-2,4-dien-1-one

The title compound, C₁₄H₁₂ClNO₃, adopts the keto–enamine tautomeric form. In the crystal, mol­ecules form stacks along the [001] direction. The crystal packing is further stabilized by O—H...O and C—H...O hydrogen bonds and C—H...Cl and C—H...π contacts.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.057
• wR factor = 0.100
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections (too) Low ..        45% Check
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full value Low .      0.974 Why?
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C2 Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00477 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7       ..CL01     .       2.88 Ang.
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......     65.933 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      9.006 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      4.443 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.440 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         61 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          4 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   9 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012)and PLATON (Spek, 2009).

(Z)-6-[(5-Chloro-2-methoxyanilino)methylidene]-2-hydroxycyclohexa-2,4-dien-1-one

Crystal data

C14H12ClNO3	F(000) = 576
Mr = 277.70	Dx = 1.420 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.7251 (9) Å	Cell parameters from 8086 reflections
b = 14.4444 (9) Å	θ = 1.4–27.1°
c = 6.1698 (4) Å	µ = 0.30 mm^−1
β = 98.241 (5)°	T = 296 K
V = 1298.74 (14) Å^3	Irregular specimen, red
Z = 4	0.23 × 0.16 × 0.09 mm

Data collection

Stoe IPDS 2 diffractometer	2491 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1120 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.115
rotation method scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −18→18
Tmin = 0.948, Tmax = 0.979	k = −17→17
13658 measured reflections	l = −7→7

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)] = 0.057	Hydrogen site location: mixed
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 0.90	w = 1/[σ^2(Fo^2) + (0.0293P)^2] where P = (Fo^2 + 2Fc^2)/3
2491 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cl01	0.49115 (8)	0.36774 (9)	−0.2476 (2)	0.1172 (6)
O1	0.11503 (15)	0.37573 (16)	−0.0556 (4)	0.0611 (6)
O2	0.10563 (15)	0.50349 (16)	0.4247 (4)	0.0601 (7)
O3	0.0461 (2)	0.5981 (2)	0.7618 (4)	0.0782 (9)
N1	0.2392 (2)	0.46609 (18)	0.2056 (5)	0.0497 (8)
C1	0.3568 (2)	0.4173 (2)	−0.0160 (6)	0.0608 (10)
H1A	0.4026	0.4475	0.0774	0.073*
C2	0.3782 (2)	0.3706 (2)	−0.1958 (6)	0.0606 (10)
C3	0.3124 (2)	0.3262 (2)	−0.3362 (6)	0.0583 (10)
H3A	0.3277	0.2961	−0.4592	0.070*
C4	0.2231 (2)	0.3264 (2)	−0.2937 (6)	0.0540 (9)
H4	0.1780	0.2953	−0.3869	0.065*
C5	0.2002 (2)	0.3725 (2)	−0.1142 (5)	0.0459 (8)
C6	0.2675 (2)	0.4193 (2)	0.0256 (5)	0.0454 (8)
C7	0.2902 (2)	0.5189 (2)	0.3445 (6)	0.0546 (9)
H7	0.3515	0.5266	0.3277	0.066*
C8	0.2572 (2)	0.5648 (2)	0.5188 (5)	0.0495 (9)
C9	0.1632 (2)	0.5551 (2)	0.5481 (5)	0.0483 (9)
C10	0.1348 (3)	0.6045 (2)	0.7269 (6)	0.0577 (9)
C11	0.1941 (3)	0.6591 (2)	0.8593 (6)	0.0669 (11)
H11	0.1733	0.6919	0.9723	0.080*
C12	0.2862 (3)	0.6667 (2)	0.8274 (6)	0.0680 (11)
H12	0.3262	0.7037	0.9205	0.082*
C13	0.3171 (3)	0.6206 (2)	0.6623 (6)	0.0619 (10)
H13	0.3784	0.6257	0.6430	0.074*
C14	0.0424 (2)	0.3301 (3)	−0.1933 (6)	0.0698 (11)
H00F	0.0378	0.3546	−0.3392	0.105*
H14B	−0.0144	0.3402	−0.1375	0.105*
H14C	0.0548	0.2649	−0.1959	0.105*
H3	0.016 (3)	0.555 (3)	0.685 (8)	0.104 (18)*
H2	0.175 (3)	0.461 (3)	0.226 (8)	0.130 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl01	0.0754 (8)	0.1458 (11)	0.1426 (12)	−0.0326 (7)	0.0573 (8)	−0.0628 (9)
O1	0.0504 (14)	0.0746 (16)	0.0578 (16)	−0.0021 (13)	0.0062 (12)	−0.0180 (13)
O2	0.0581 (15)	0.0667 (16)	0.0544 (17)	−0.0025 (13)	0.0051 (13)	−0.0148 (12)
O3	0.077 (2)	0.087 (2)	0.074 (2)	0.0025 (16)	0.0234 (17)	−0.0277 (16)
N1	0.0535 (19)	0.0501 (19)	0.047 (2)	−0.0040 (14)	0.0114 (17)	−0.0032 (14)
C1	0.063 (3)	0.060 (2)	0.061 (3)	−0.0134 (17)	0.014 (2)	−0.0135 (18)
C2	0.061 (2)	0.057 (2)	0.068 (3)	−0.011 (2)	0.025 (2)	−0.010 (2)
C3	0.073 (3)	0.050 (2)	0.056 (3)	0.001 (2)	0.019 (2)	−0.0059 (19)
C4	0.060 (3)	0.048 (2)	0.053 (2)	−0.0013 (17)	0.005 (2)	−0.0097 (17)
C5	0.051 (2)	0.043 (2)	0.044 (2)	0.0025 (17)	0.0085 (18)	0.0000 (17)
C6	0.055 (2)	0.041 (2)	0.041 (2)	−0.0018 (16)	0.0093 (19)	−0.0023 (15)
C7	0.059 (2)	0.052 (2)	0.053 (2)	−0.0125 (18)	0.010 (2)	−0.0031 (19)
C8	0.063 (2)	0.042 (2)	0.043 (2)	−0.0008 (16)	0.0073 (19)	−0.0044 (16)
C9	0.067 (2)	0.0347 (19)	0.042 (2)	0.0064 (17)	0.004 (2)	−0.0009 (16)
C10	0.072 (3)	0.050 (2)	0.052 (2)	0.007 (2)	0.011 (2)	−0.0005 (19)
C11	0.093 (3)	0.056 (3)	0.053 (3)	0.007 (2)	0.015 (2)	−0.0073 (19)
C12	0.088 (3)	0.058 (2)	0.055 (3)	−0.011 (2)	0.000 (2)	−0.015 (2)
C13	0.074 (2)	0.054 (2)	0.057 (3)	−0.010 (2)	0.008 (2)	−0.0087 (19)
C14	0.053 (2)	0.095 (3)	0.060 (3)	−0.002 (2)	0.002 (2)	−0.010 (2)

Geometric parameters (Å, º)

Cl01—C2	1.739 (3)	C4—H4	0.9300
O1—C5	1.354 (3)	C5—C6	1.393 (4)
O1—C14	1.429 (4)	C7—C8	1.408 (4)
O2—C9	1.292 (4)	C7—H7	0.9300
O3—C10	1.358 (4)	C8—C9	1.429 (4)
O3—H3	0.87 (4)	C8—C13	1.410 (5)
N1—C6	1.413 (4)	C9—C10	1.426 (4)
N1—C7	1.302 (4)	C10—C11	1.359 (5)
N1—H2	0.97 (4)	C11—C12	1.402 (5)
C1—C2	1.372 (4)	C11—H11	0.9300
C1—C6	1.376 (4)	C12—C13	1.349 (4)
C1—H1A	0.9300	C12—H12	0.9300
C2—C3	1.363 (5)	C13—H13	0.9300
C3—C4	1.379 (4)	C14—H00F	0.9600
C3—H3A	0.9300	C14—H14B	0.9600
C4—C5	1.375 (4)	C14—H14C	0.9600
C5—O1—C14	117.9 (3)	C8—C7—H7	118.3
C10—O3—H3	113 (3)	C7—C8—C13	119.7 (3)
C7—N1—C6	126.1 (3)	C7—C8—C9	119.8 (3)
C7—N1—H2	116 (3)	C13—C8—C9	120.4 (3)
C6—N1—H2	118 (3)	O2—C9—C10	120.3 (3)
C2—C1—C6	119.8 (3)	O2—C9—C8	123.2 (3)
C2—C1—H1A	120.1	C10—C9—C8	116.5 (3)
C6—C1—H1A	120.1	O3—C10—C11	119.6 (3)
C3—C2—C1	121.4 (3)	O3—C10—C9	118.9 (4)
C3—C2—Cl01	118.9 (3)	C11—C10—C9	121.4 (3)
C1—C2—Cl01	119.7 (3)	C10—C11—C12	120.8 (3)
C2—C3—C4	119.2 (3)	C10—C11—H11	119.6
C2—C3—H3A	120.4	C12—C11—H11	119.6
C4—C3—H3A	120.4	C13—C12—C11	120.3 (4)
C5—C4—C3	120.4 (3)	C13—C12—H12	119.8
C5—C4—H4	119.8	C11—C12—H12	119.8
C3—C4—H4	119.8	C12—C13—C8	120.5 (3)
O1—C5—C4	125.1 (3)	C12—C13—H13	119.7
O1—C5—C6	115.0 (3)	C8—C13—H13	119.7
C4—C5—C6	119.9 (3)	O1—C14—H00F	109.5
C1—C6—C5	119.3 (3)	O1—C14—H14B	109.5
C1—C6—N1	123.7 (3)	H00F—C14—H14B	109.5
C5—C6—N1	117.0 (3)	O1—C14—H14C	109.5
N1—C7—C8	123.3 (3)	H00F—C14—H14C	109.5
N1—C7—H7	118.3	H14B—C14—H14C	109.5
C6—C1—C2—C3	0.3 (6)	C6—N1—C7—C8	179.0 (3)
C6—C1—C2—Cl01	−179.7 (3)	N1—C7—C8—C13	179.9 (3)
C1—C2—C3—C4	−1.5 (6)	N1—C7—C8—C9	−0.6 (5)
Cl01—C2—C3—C4	178.6 (3)	C7—C8—C9—O2	2.0 (5)
C2—C3—C4—C5	1.3 (5)	C13—C8—C9—O2	−178.5 (3)
C14—O1—C5—C4	−1.8 (5)	C7—C8—C9—C10	−179.3 (3)
C14—O1—C5—C6	179.2 (3)	C13—C8—C9—C10	0.1 (5)
C3—C4—C5—O1	−178.8 (3)	O2—C9—C10—O3	−1.5 (5)
C3—C4—C5—C6	0.1 (5)	C8—C9—C10—O3	179.8 (3)
C2—C1—C6—C5	1.0 (5)	O2—C9—C10—C11	179.8 (3)
C2—C1—C6—N1	−179.5 (3)	C8—C9—C10—C11	1.2 (5)
O1—C5—C6—C1	177.8 (3)	O3—C10—C11—C12	179.7 (3)
C4—C5—C6—C1	−1.2 (5)	C9—C10—C11—C12	−1.7 (6)
O1—C5—C6—N1	−1.7 (4)	C10—C11—C12—C13	0.9 (6)
C4—C5—C6—N1	179.3 (3)	C11—C12—C13—C8	0.4 (6)
C7—N1—C6—C1	5.8 (5)	C7—C8—C13—C12	178.6 (3)
C7—N1—C6—C5	−174.7 (3)	C9—C8—C13—C12	−0.9 (5)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl01^i	0.93	2.88	3.737 (3)	154
C14—H14B···O3^ii	0.96	2.59	3.295 (4)	131
O3—H3···O2^ii	0.87 (4)	2.00 (4)	2.780 (4)	148 (4)
N1—H2···O2	0.97 (4)	1.82 (4)	2.598 (3)	136 (4)
C3—H3A···Cg1^iii	0.93	2.73	3.463 (3)	136

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