Crystal structure of 3-{(E)-[(3,4-di­chloro­phen­yl)imino]­meth­yl}benzene-1,2-diol

In the title Schiff base, C₁₃H₉Cl₂NO₂, which arose from the condensation of 3,4-di­chloro­aniline with 2,3-di­hydroxy­benzaldehyde, the dihedral angle between the aromatic rings is 44.74 (13)°. Intra­molecular O—H...O and O—H...N hydrogen bonds close S(5) and S(6) rings, respectively. In the crystal, inversion dimers linked by pairs of O—H...O hydrogen bonds generate R₂²(10) loops. A weak C—H...π inter­action is also observed.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.164
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

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Alert level C
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0044 Ang.
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........        CGL
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.980 Report
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2 Report

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT434_ALERT_2_G Short Inter HL..HL Contact Cl2    ..  Cl2     ..       3.34 Ang.
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note

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

   3 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
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

The title compound (I), (Fig. 1) has been synthesized for forming different metal complexes.

The crystal structures of 2-[(E)-(2,4,6-trichlorophenyl)iminomethyl] phenol (Fun et al., 2011), (E)-3-((2-fluorophenylimino)methyl) benzene-1,2-diol (Temel et al., 2007), (E)-3-[(3-bromophenyl) iminomethyl]benzene-1,2-diol (Kelesoglu et al., 2009), 4-([(E)-2, 3-dihydroxybenzylidene]amino)-N-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide (Tahir et al., 2012) and 3-(4-bromophenyliminomethyl)benzene-1,2-diol (Shuja et al., 2006) have been published which are related to the title compound due to two moieties of the Schiff base.

In (I) the moieties of 2,3-dihydroxybenzaldehyde A (C1–C7/O1/O2) and 3,4-dichloroanilline B (C8—13/N1/CL1/CL2) are almost planar with r.m.s. deviation of 0.0225 and 0.0172 Å, respectively. The dihedral angle between A/B is 44.219 (50)°. In (I), S(5) and S(6) ring motifs are present due to H-bondings of O—H···O and O—H···N types (Table 1, Fig. 2). The molecules are dimerized due to bifercated H-bonding of O—H···O type (Table 1, Fig. 2). There exist C—H···π (Table 1) and π···π interactions to stablize the dimmers. A π···π interactions between Cg1···Cg1ⁱ [i = -x, 2 - y, 1 - z] at a distance of 3.9101 (15) Å, where Cg1 is centroid of benzene ring (C1—C6) exists. Similarly, there is π···π interactions between Cg2···Cg2ⁱⁱ [il = 1 - x, 1 - y, - z] at a distance of 4.1194 (17) Å, where Cg2 is centroid of benzene ring (C8—C13).

Related literature

For related structures, see: Fun et al. (2011); Kelesoglu et al. (2009); Shuja et al. (2006); Tahir et al. (2012); Temel et al. (2007).

S2. Experimental

Equimolar quantities of 3,4-dichloroanilline and 2,3-dihydroxybenzaldehyde were refluxed in methanol for 2 h. The resulting mixture was evaporated to grow crystals. Red prisms were obtained after 48 h.

S3. Refinement

The H-atoms were positioned geometrically (C–H = 0.93 Å, O—H = 0.82 Å) and refined as riding with U_iso(H) = xU_eq(C, O), where x = 1.5 for hydroxy and x = 1.2 for other H-atoms.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing (PLATON; Spek, 2009), which shows that molecules form dimers due to O—H···O interactions.

3-{(E)-[(3,4-Dichlorophenyl)imino]methyl}benzene-1,2-diol

Crystal data

C13H9Cl2NO2	Z = 2
Mr = 282.11	F(000) = 284
Triclinic, P1	Dx = 1.533 Mg m^−3
a = 6.4237 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8412 (11) Å	Cell parameters from 1866 reflections
c = 11.7799 (15) Å	θ = 1.8–27.0°
α = 88.606 (6)°	µ = 0.52 mm^−1
β = 76.588 (6)°	T = 296 K
γ = 70.193 (5)°	Prism, red
V = 611.20 (13) Å^3	0.34 × 0.26 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2671 independent reflections
Radiation source: fine-focus sealed tube	1866 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 7.80 pixels mm^-1	θmax = 27.0°, θmin = 1.8°
ω scans	h = −8→7
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −11→9
Tmin = 0.844, Tmax = 0.902	l = −14→15
8896 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0781P)^2 + 0.3755P] where P = (Fo^2 + 2Fc^2)/3
2671 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.33 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
Cl1	0.24642 (15)	0.26936 (10)	0.01956 (8)	0.0657 (3)
Cl2	0.73742 (15)	0.11968 (10)	0.06575 (9)	0.0707 (3)
O1	−0.2559 (3)	0.9592 (2)	0.38833 (19)	0.0508 (5)
H1	−0.1671	0.8794	0.3473	0.076*
O2	−0.4973 (3)	1.2453 (3)	0.5138 (2)	0.0594 (6)
H2	−0.5353	1.1679	0.5037	0.089*
N1	0.1345 (4)	0.7735 (3)	0.2617 (2)	0.0452 (6)
C1	−0.1526 (5)	1.0707 (3)	0.3887 (2)	0.0388 (6)
C2	−0.2793 (5)	1.2167 (3)	0.4525 (2)	0.0440 (6)
C3	−0.1834 (5)	1.3338 (3)	0.4543 (2)	0.0478 (7)
H3	−0.2694	1.4313	0.4964	0.057*
C4	0.0401 (5)	1.3083 (4)	0.3943 (3)	0.0516 (7)
H4	0.1030	1.3886	0.3954	0.062*
C5	0.1694 (5)	1.1613 (4)	0.3322 (3)	0.0494 (7)
H5	0.3201	1.1427	0.2932	0.059*
C6	0.0738 (5)	1.0419 (3)	0.3285 (2)	0.0409 (6)
C7	0.2124 (5)	0.8875 (3)	0.2674 (2)	0.0440 (6)
H7	0.3638	0.8708	0.2309	0.053*
C8	0.2859 (5)	0.6190 (3)	0.2123 (2)	0.0433 (6)
C9	0.2070 (5)	0.5315 (3)	0.1462 (2)	0.0464 (7)
H9	0.0614	0.5751	0.1334	0.056*
C10	0.3479 (5)	0.3784 (3)	0.0998 (2)	0.0447 (6)
C11	0.5634 (5)	0.3123 (3)	0.1205 (2)	0.0471 (7)
C12	0.6396 (5)	0.3969 (4)	0.1879 (3)	0.0490 (7)
H12	0.7834	0.3514	0.2027	0.059*
C13	0.5000 (5)	0.5513 (3)	0.2339 (2)	0.0480 (7)
H13	0.5511	0.6091	0.2793	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0749 (6)	0.0607 (5)	0.0663 (5)	−0.0278 (4)	−0.0167 (4)	−0.0188 (4)
Cl2	0.0675 (6)	0.0459 (5)	0.0815 (6)	−0.0049 (4)	−0.0040 (4)	−0.0243 (4)
O1	0.0505 (11)	0.0377 (10)	0.0591 (13)	−0.0162 (9)	0.0005 (9)	−0.0157 (9)
O2	0.0502 (12)	0.0463 (12)	0.0765 (15)	−0.0184 (10)	0.0001 (11)	−0.0216 (11)
N1	0.0488 (13)	0.0387 (12)	0.0405 (12)	−0.0089 (10)	−0.0041 (10)	−0.0057 (10)
C1	0.0451 (14)	0.0348 (13)	0.0361 (13)	−0.0133 (11)	−0.0086 (11)	−0.0023 (10)
C2	0.0503 (16)	0.0365 (14)	0.0419 (14)	−0.0111 (12)	−0.0094 (12)	−0.0072 (11)
C3	0.0619 (18)	0.0362 (14)	0.0423 (15)	−0.0117 (13)	−0.0133 (13)	−0.0077 (12)
C4	0.067 (2)	0.0455 (16)	0.0519 (17)	−0.0291 (15)	−0.0173 (15)	0.0016 (13)
C5	0.0536 (17)	0.0495 (16)	0.0469 (16)	−0.0240 (14)	−0.0058 (13)	−0.0009 (13)
C6	0.0489 (15)	0.0346 (13)	0.0355 (13)	−0.0114 (12)	−0.0070 (11)	−0.0001 (11)
C7	0.0473 (15)	0.0405 (14)	0.0372 (14)	−0.0113 (12)	−0.0016 (11)	−0.0053 (11)
C8	0.0508 (16)	0.0365 (14)	0.0359 (14)	−0.0124 (12)	−0.0007 (12)	−0.0059 (11)
C9	0.0490 (16)	0.0435 (15)	0.0442 (15)	−0.0146 (13)	−0.0073 (12)	−0.0045 (12)
C10	0.0531 (16)	0.0436 (15)	0.0373 (14)	−0.0198 (13)	−0.0051 (12)	−0.0047 (11)
C11	0.0524 (16)	0.0396 (14)	0.0406 (15)	−0.0113 (13)	0.0001 (12)	−0.0070 (12)
C12	0.0469 (16)	0.0486 (16)	0.0463 (16)	−0.0102 (13)	−0.0094 (13)	−0.0060 (13)
C13	0.0546 (17)	0.0455 (16)	0.0422 (15)	−0.0160 (13)	−0.0089 (13)	−0.0103 (12)

Geometric parameters (Å, º)

Cl1—C10	1.733 (3)	C4—H4	0.9300
Cl2—C11	1.731 (3)	C5—C6	1.396 (4)
O1—C1	1.363 (3)	C5—H5	0.9300
O1—H1	0.8200	C6—C7	1.450 (4)
O2—C2	1.359 (3)	C7—H7	0.9300
O2—H2	0.8200	C8—C13	1.383 (4)
N1—C7	1.277 (4)	C8—C9	1.392 (4)
N1—C8	1.423 (3)	C9—C10	1.388 (4)
C1—C2	1.394 (4)	C9—H9	0.9300
C1—C6	1.401 (4)	C10—C11	1.385 (4)
C2—C3	1.375 (4)	C11—C12	1.373 (4)
C3—C4	1.390 (4)	C12—C13	1.394 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.395 (4)	C13—H13	0.9300
C1—O1—H1	109.5	N1—C7—C6	122.5 (3)
C2—O2—H2	109.5	N1—C7—H7	118.7
C7—N1—C8	119.6 (2)	C6—C7—H7	118.7
O1—C1—C2	117.8 (2)	C13—C8—C9	119.9 (2)
O1—C1—C6	122.1 (2)	C13—C8—N1	122.1 (3)
C2—C1—C6	120.1 (2)	C9—C8—N1	117.9 (3)
O2—C2—C3	119.1 (2)	C10—C9—C8	119.3 (3)
O2—C2—C1	120.9 (2)	C10—C9—H9	120.3
C3—C2—C1	120.0 (3)	C8—C9—H9	120.3
C2—C3—C4	120.9 (3)	C11—C10—C9	120.3 (3)
C2—C3—H3	119.6	C11—C10—Cl1	120.7 (2)
C4—C3—H3	119.6	C9—C10—Cl1	118.9 (2)
C3—C4—C5	119.5 (3)	C12—C11—C10	120.5 (3)
C3—C4—H4	120.3	C12—C11—Cl2	118.9 (2)
C5—C4—H4	120.3	C10—C11—Cl2	120.6 (2)
C4—C5—C6	120.3 (3)	C11—C12—C13	119.5 (3)
C4—C5—H5	119.8	C11—C12—H12	120.2
C6—C5—H5	119.8	C13—C12—H12	120.2
C5—C6—C1	119.3 (2)	C8—C13—C12	120.4 (3)
C5—C6—C7	119.8 (3)	C8—C13—H13	119.8
C1—C6—C7	120.9 (2)	C12—C13—H13	119.8
O1—C1—C2—O2	1.1 (4)	C1—C6—C7—N1	2.5 (4)
C6—C1—C2—O2	−178.3 (3)	C7—N1—C8—C13	40.5 (4)
O1—C1—C2—C3	−179.2 (3)	C7—N1—C8—C9	−143.4 (3)
C6—C1—C2—C3	1.4 (4)	C13—C8—C9—C10	−1.9 (4)
O2—C2—C3—C4	179.0 (3)	N1—C8—C9—C10	−178.1 (2)
C1—C2—C3—C4	−0.7 (4)	C8—C9—C10—C11	1.0 (4)
C2—C3—C4—C5	−0.6 (4)	C8—C9—C10—Cl1	179.0 (2)
C3—C4—C5—C6	1.3 (5)	C9—C10—C11—C12	0.5 (4)
C4—C5—C6—C1	−0.7 (4)	Cl1—C10—C11—C12	−177.5 (2)
C4—C5—C6—C7	−177.7 (3)	C9—C10—C11—Cl2	178.5 (2)
O1—C1—C6—C5	179.9 (3)	Cl1—C10—C11—Cl2	0.5 (4)
C2—C1—C6—C5	−0.7 (4)	C10—C11—C12—C13	−1.1 (4)
O1—C1—C6—C7	−3.1 (4)	Cl2—C11—C12—C13	−179.1 (2)
C2—C1—C6—C7	176.3 (3)	C9—C8—C13—C12	1.3 (4)
C8—N1—C7—C6	−172.6 (2)	N1—C8—C13—C12	177.3 (3)
C5—C6—C7—N1	179.5 (3)	C11—C12—C13—C8	0.2 (4)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the benzene ring (C1–C6).

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.89	2.608 (3)	146
O2—H2···O1	0.82	2.28	2.729 (3)	115
O2—H2···O1^i	0.82	2.20	2.846 (3)	136
C12—H12···Cg1^ii	0.93	2.83	3.538 (4)	134

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