2-[(Z)-(2,5-Dichloro­phen­yl)imino­methyl]-5-(diethyl­amino)phenol

In the title mol­ecule, C₁₇H₁₈Cl₂N₂O, the angle between the mean planes of the 2,5-dichloro­phenyl­imino and phenol groups is 19.5 (5)°. The two ethyl groups adopt a synclinal conformation. The crystal structure is stabilized by inter­molecular π–π stacking inter­actions between adjacent 2,5-dichloro­phenyl rings, the distance between the centroids of inter­acting rings being 3.860 (8) Å. The mol­ecules are stacked parallel to the a axis. In addition, an O—H...N intra­molecular hydrogen-bonding inter­action between the phenol H atom and imino N atom is observed.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.120
• Data-to-parameter ratio = 27.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.720     0.927
            Tmin(prime) and Tmax expected:      0.807     0.927
            RR(prime) =      0.892
            Please check that your absorption correction is appropriate.
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         48 Perc.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.89

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Schiff bases are synthesized from an aromatic amine and a carbonyl compound by a nucleophilic addition reaction. They are used as substrates in the preparation of number of biologically active compounds (Siddiqui et al., 2006). Some Schiff base derivatives are also known to have activities such as antimicrobial (El-Masry et al., 2000; Pandey et al., 1999), antifungal (Singh & Dash, 1988; Varma et al., 1986), antitumor (Hodnett & Dunn, 1970; Misra et al., 1981; Agarwal et al., 1983) and as herbicides (Samadhiya & Halve, 2001). The crystal structures of (E)-2-hydroxy-5-methyl-3-[(4-methyl-2 pyridyl)iminomethyl] benzaldehyde (Büyükgüngör et al., 2007), (E)-2-hydroxy-5-methyl-3-[(2-pyridylimino) methyl]benzaldehyde (Odabaşoğlu et al., 2007), 1-(4-{[(E)-(4-diethylamino-2-hydroxy phenyl)methylene]amino} phenyl)ethanone (Yathirajan et al., (2007), 2-{(E)-[(2-chloro-5-nitrophenyl)imino]methyl}-5-(diethylamino)phenol (Butcher et al., 2007) have been reported. A new Schiff base, (I), C₁₇H₁₈Cl₂N₂O is prepared and its crystal structure is reported.

The angle between the mean planes of the 2,5-dichlorophenyl-imino and phenol groups is 19.5 (5)° Fig. 1). The two ethyl groups adopt a syn-clinal conformation [C11—N2—C14—C15 = -87.9 (2)°; C11—N2—C16—C17 = -87.58 (19)°]. Crystal packing is stabilized by intermolecular π stacking interactions between Cg1ⁱ-π orbitals of nearby 2,5-dichlorolphenyl rings [Cg1···Cg1 = 3.860 (8) Å; Cg1 = center of gravity of the 2,5-dichlorophenyl ring (Fig. 2)]. The molecules are aligned in an inverted pattern along the c axis with the with the 2,5-dichlorophenyl rings stacked obliquely parallel to the ac face of the unit cell (Fig. 3). Intramolecular hydrogen bonding interactions [O1—H10···N1] between the phenol hydrogen atom and imino nitrogen atom provides additional crystal stability within the asymmetric unit. [i = 2 - x, -y, 2 - z].

Related literature

For related structures, see: Büyükgüngör et al. (2007); Odabaşoğlu et al. (2007); Yathirajan et al. (2007); Butcher et al. (2007). For related literature, see: Hodnett & Dunn (1970); Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988); Pandey et al. (1999); El-Masry et al. (2000); Samadhiya & Halve (2001); Siddiqui et al. (2006).

S2. Experimental

A mixture of 2,5-dichloroaniline (1.62 g, 0.01 mol) and 4-(diethylamino)-2-hydroxybenzaldehyde (1.93 g, 0.01 mol) in 30 ml of ethanol containing 2 drops of 4 M sulfuric acid was refluxed for about 7 h (Fig. 4). On cooling, the solid separated was filtered and recrystallized from acetone (m.p.: 397–401 K). Analysis found: C 60.46, H 5.32, N 8.24%; C₁₇H₁₈C_l2N₂O requires: C 60.54, H 5.38, N 8.31%.

S3. Refinement

The hydroxyl atom (H10) was located in a difference Fourier map and along with all other H atoms were placed in their calculated positions and then refined using the riding model with O—H = 0.82 Å and C—H = 0.93 to 0.97 Å, and with U_iso(H) = 1.19–1.49U_eq(C, O).

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. Molecular structure of the title compound, showing atom labeling and 50% probability displacement ellipsoids. The dashed line indicates the intramolecular O—H···N hydrogen bond.
	Fig. 2. Packing diagram of the title compound, viewed down the a axis.
	Fig. 3. Packing diagram of the title compound, viewed down the b axis. Dashed lines indicate intramolecular O—H···N hydrogen bonds.
	Fig. 4. Synthetic scheme for C17H18Cl2N2O.

2-[(Z)-(2,5-Dichlorophenyl)iminomethyl]-5-(diethylamino)phenol

Crystal data

C17H18Cl2N2O	F(000) = 704
Mr = 337.23	Dx = 1.367 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4869 reflections
a = 7.1729 (2) Å	θ = 4.7–32.5°
b = 18.6396 (6) Å	µ = 0.40 mm^−1
c = 12.6378 (4) Å	T = 296 K
β = 104.157 (3)°	Thick needle, pale yellow
V = 1638.36 (9) Å^3	0.53 × 0.25 × 0.19 mm
Z = 4

Data collection

Oxford Diffraction Gemini R CCD diffractometer	5491 independent reflections
Radiation source: fine-focus sealed tube	2626 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 10.5081 pixels mm^-1	θmax = 32.5°, θmin = 4.7°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −27→27
Tmin = 0.720, Tmax = 0.927	l = −18→19
17605 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.055P)^2] where P = (Fo^2 + 2Fc^2)/3
5491 reflections	(Δ/σ)max = 0.003
202 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.31 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	0.43274 (6)	0.45456 (3)	0.77923 (4)	0.06735 (16)
Cl2	−0.37011 (6)	0.41423 (3)	0.46310 (4)	0.06539 (16)
O1	0.30792 (15)	0.59856 (7)	0.95939 (10)	0.0573 (3)
H1O	0.2780	0.5722	0.9060	0.069*
N1	0.07935 (18)	0.52207 (6)	0.80838 (10)	0.0435 (3)
N2	0.0292 (2)	0.73892 (7)	1.19527 (11)	0.0532 (3)
C1	0.0490 (2)	0.47783 (7)	0.71617 (12)	0.0398 (3)
C2	0.2079 (2)	0.44459 (8)	0.69148 (13)	0.0443 (4)
C3	0.1895 (3)	0.40261 (9)	0.59958 (14)	0.0547 (4)
H3A	0.2976	0.3812	0.5849	0.066*
C4	0.0108 (3)	0.39229 (9)	0.52911 (14)	0.0539 (4)
H4A	−0.0033	0.3636	0.4674	0.065*
C5	−0.1452 (2)	0.42544 (8)	0.55252 (12)	0.0458 (4)
C6	−0.1297 (2)	0.46767 (8)	0.64337 (12)	0.0433 (3)
H6A	−0.2385	0.4895	0.6564	0.052*
C7	−0.0578 (2)	0.53797 (8)	0.85377 (12)	0.0441 (4)
H7A	−0.1774	0.5166	0.8277	0.053*
C8	−0.0324 (2)	0.58710 (8)	0.94251 (12)	0.0411 (3)
C9	0.1485 (2)	0.61728 (8)	0.99181 (12)	0.0422 (3)
C10	0.1682 (2)	0.66657 (8)	1.07560 (13)	0.0474 (4)
H10A	0.2889	0.6856	1.1070	0.057*
C11	0.0095 (2)	0.68848 (8)	1.11419 (12)	0.0439 (4)
C12	−0.1712 (2)	0.65751 (8)	1.06588 (13)	0.0484 (4)
H12A	−0.2790	0.6707	1.0899	0.058*
C13	−0.1882 (2)	0.60832 (8)	0.98419 (13)	0.0474 (4)
H13A	−0.3081	0.5880	0.9548	0.057*
C14	0.2107 (3)	0.77568 (9)	1.24016 (14)	0.0550 (4)
H14A	0.1839	0.8229	1.2650	0.066*
H14B	0.2776	0.7820	1.1828	0.066*
C15	0.3403 (3)	0.73581 (11)	1.33400 (16)	0.0708 (5)
H15A	0.4551	0.7632	1.3618	0.106*
H15B	0.3737	0.6901	1.3090	0.106*
H15C	0.2746	0.7288	1.3909	0.106*
C16	−0.1285 (3)	0.75621 (9)	1.24523 (14)	0.0548 (4)
H16A	−0.0757	0.7719	1.3197	0.066*
H16B	−0.2035	0.7132	1.2477	0.066*
C17	−0.2591 (3)	0.81395 (10)	1.18432 (16)	0.0647 (5)
H17A	−0.3574	0.8245	1.2217	0.097*
H17B	−0.3177	0.7976	1.1117	0.097*
H17C	−0.1855	0.8565	1.1807	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0356 (2)	0.1007 (4)	0.0625 (3)	0.0009 (2)	0.00571 (19)	−0.0005 (2)
Cl2	0.0521 (3)	0.0786 (3)	0.0573 (3)	−0.0096 (2)	−0.0023 (2)	−0.0120 (2)
O1	0.0354 (6)	0.0763 (8)	0.0580 (8)	0.0022 (5)	0.0073 (5)	−0.0187 (6)
N1	0.0392 (7)	0.0453 (7)	0.0430 (7)	0.0010 (6)	0.0047 (5)	−0.0007 (5)
N2	0.0458 (8)	0.0567 (8)	0.0551 (9)	0.0044 (6)	0.0086 (6)	−0.0122 (6)
C1	0.0394 (8)	0.0400 (7)	0.0390 (8)	−0.0030 (6)	0.0077 (6)	0.0033 (6)
C2	0.0343 (8)	0.0548 (9)	0.0433 (9)	−0.0019 (7)	0.0088 (6)	0.0063 (7)
C3	0.0462 (10)	0.0688 (11)	0.0533 (10)	0.0061 (8)	0.0202 (8)	0.0015 (8)
C4	0.0577 (11)	0.0601 (10)	0.0461 (10)	−0.0042 (9)	0.0170 (8)	−0.0085 (7)
C5	0.0420 (9)	0.0507 (9)	0.0420 (9)	−0.0074 (7)	0.0048 (7)	0.0000 (7)
C6	0.0381 (8)	0.0455 (8)	0.0455 (9)	0.0012 (7)	0.0088 (6)	0.0006 (6)
C7	0.0380 (8)	0.0453 (8)	0.0455 (9)	−0.0056 (7)	0.0038 (6)	0.0021 (7)
C8	0.0370 (8)	0.0433 (8)	0.0412 (8)	−0.0031 (6)	0.0065 (6)	0.0035 (6)
C9	0.0349 (8)	0.0453 (8)	0.0436 (8)	0.0038 (7)	0.0043 (6)	0.0028 (6)
C10	0.0358 (8)	0.0533 (9)	0.0486 (9)	−0.0021 (7)	0.0017 (7)	−0.0024 (7)
C11	0.0425 (9)	0.0440 (8)	0.0424 (9)	0.0035 (7)	0.0048 (7)	0.0021 (6)
C12	0.0396 (9)	0.0541 (9)	0.0526 (10)	0.0017 (7)	0.0134 (7)	0.0006 (7)
C13	0.0382 (8)	0.0518 (9)	0.0518 (10)	−0.0090 (7)	0.0103 (7)	−0.0022 (7)
C14	0.0587 (11)	0.0498 (9)	0.0528 (10)	−0.0009 (8)	0.0065 (8)	−0.0075 (7)
C15	0.0641 (12)	0.0752 (12)	0.0644 (12)	0.0043 (10)	−0.0014 (10)	−0.0011 (10)
C16	0.0593 (11)	0.0566 (10)	0.0490 (10)	0.0041 (8)	0.0144 (8)	−0.0022 (7)
C17	0.0571 (11)	0.0673 (11)	0.0693 (12)	0.0124 (9)	0.0149 (9)	0.0008 (9)

Geometric parameters (Å, º)

Cl1—C2	1.7293 (16)	C8—C9	1.411 (2)
Cl2—C5	1.7412 (16)	C9—C10	1.383 (2)
O1—C9	1.3516 (17)	C10—C11	1.404 (2)
O1—H1O	0.8200	C10—H10A	0.9300
N1—C7	1.2885 (19)	C11—C12	1.414 (2)
N1—C1	1.4005 (18)	C12—C13	1.364 (2)
N2—C11	1.372 (2)	C12—H12A	0.9300
N2—C14	1.457 (2)	C13—H13A	0.9300
N2—C16	1.461 (2)	C14—C15	1.511 (2)
C1—C6	1.396 (2)	C14—H14A	0.9700
C1—C2	1.398 (2)	C14—H14B	0.9700
C2—C3	1.380 (2)	C15—H15A	0.9600
C3—C4	1.384 (2)	C15—H15B	0.9600
C3—H3A	0.9300	C15—H15C	0.9600
C4—C5	1.372 (2)	C16—C17	1.508 (2)
C4—H4A	0.9300	C16—H16A	0.9700
C5—C6	1.374 (2)	C16—H16B	0.9700
C6—H6A	0.9300	C17—H17A	0.9600
C7—C8	1.425 (2)	C17—H17B	0.9600
C7—H7A	0.9300	C17—H17C	0.9600
C8—C13	1.404 (2)
C9—O1—H1O	109.5	C11—C10—H10A	119.4
C7—N1—C1	121.73 (13)	N2—C11—C10	120.95 (14)
C11—N2—C14	122.14 (14)	N2—C11—C12	121.22 (14)
C11—N2—C16	121.65 (14)	C10—C11—C12	117.83 (14)
C14—N2—C16	116.15 (14)	C13—C12—C11	120.25 (15)
C6—C1—C2	117.40 (14)	C13—C12—H12A	119.9
C6—C1—N1	123.98 (13)	C11—C12—H12A	119.9
C2—C1—N1	118.53 (13)	C12—C13—C8	122.81 (15)
C3—C2—C1	121.60 (15)	C12—C13—H13A	118.6
C3—C2—Cl1	118.88 (12)	C8—C13—H13A	118.6
C1—C2—Cl1	119.51 (12)	N2—C14—C15	113.20 (15)
C2—C3—C4	120.22 (15)	N2—C14—H14A	108.9
C2—C3—H3A	119.9	C15—C14—H14A	108.9
C4—C3—H3A	119.9	N2—C14—H14B	108.9
C5—C4—C3	118.33 (15)	C15—C14—H14B	108.9
C5—C4—H4A	120.8	H14A—C14—H14B	107.8
C3—C4—H4A	120.8	C14—C15—H15A	109.5
C4—C5—C6	122.32 (15)	C14—C15—H15B	109.5
C4—C5—Cl2	118.75 (13)	H15A—C15—H15B	109.5
C6—C5—Cl2	118.93 (12)	C14—C15—H15C	109.5
C5—C6—C1	120.12 (14)	H15A—C15—H15C	109.5
C5—C6—H6A	119.9	H15B—C15—H15C	109.5
C1—C6—H6A	119.9	N2—C16—C17	112.77 (14)
N1—C7—C8	122.27 (14)	N2—C16—H16A	109.0
N1—C7—H7A	118.9	C17—C16—H16A	109.0
C8—C7—H7A	118.9	N2—C16—H16B	109.0
C13—C8—C9	116.88 (14)	C17—C16—H16B	109.0
C13—C8—C7	121.09 (14)	H16A—C16—H16B	107.8
C9—C8—C7	122.03 (14)	C16—C17—H17A	109.5
O1—C9—C10	117.90 (13)	C16—C17—H17B	109.5
O1—C9—C8	121.19 (13)	H17A—C17—H17B	109.5
C10—C9—C8	120.91 (14)	C16—C17—H17C	109.5
C9—C10—C11	121.29 (14)	H17A—C17—H17C	109.5
C9—C10—H10A	119.4	H17B—C17—H17C	109.5
C7—N1—C1—C6	23.4 (2)	C13—C8—C9—C10	−1.4 (2)
C7—N1—C1—C2	−160.16 (14)	C7—C8—C9—C10	177.95 (14)
C6—C1—C2—C3	−0.7 (2)	O1—C9—C10—C11	−179.71 (14)
N1—C1—C2—C3	−177.40 (14)	C8—C9—C10—C11	−0.2 (2)
C6—C1—C2—Cl1	−179.43 (11)	C14—N2—C11—C10	4.2 (2)
N1—C1—C2—Cl1	3.92 (18)	C16—N2—C11—C10	−172.72 (15)
C1—C2—C3—C4	−0.2 (2)	C14—N2—C11—C12	−175.03 (15)
Cl1—C2—C3—C4	178.53 (13)	C16—N2—C11—C12	8.0 (2)
C2—C3—C4—C5	0.8 (2)	C9—C10—C11—N2	−178.16 (14)
C3—C4—C5—C6	−0.5 (2)	C9—C10—C11—C12	1.1 (2)
C3—C4—C5—Cl2	178.80 (12)	N2—C11—C12—C13	178.94 (15)
C4—C5—C6—C1	−0.4 (2)	C10—C11—C12—C13	−0.3 (2)
Cl2—C5—C6—C1	−179.72 (11)	C11—C12—C13—C8	−1.4 (2)
C2—C1—C6—C5	1.0 (2)	C9—C8—C13—C12	2.2 (2)
N1—C1—C6—C5	177.46 (13)	C7—C8—C13—C12	−177.13 (15)
C1—N1—C7—C8	−175.23 (13)	C11—N2—C14—C15	−87.9 (2)
N1—C7—C8—C13	174.32 (14)	C16—N2—C14—C15	89.23 (18)
N1—C7—C8—C9	−5.0 (2)	C11—N2—C16—C17	−87.58 (19)
C13—C8—C9—O1	178.08 (14)	C14—N2—C16—C17	95.31 (19)
C7—C8—C9—O1	−2.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.82	1.89	2.6139 (16)	147