6,6'-Dimeth-oxy-2,2'-[(E,E')-(4-chloro-m-phenyl-ene)bis-(nitrilo-methyl-idyne)]diphenol.

The title compound, C(22)H(19)ClN(2)O(4), has the appearance of a warped butterfly. One 2-hydr-oxy-3-methoxy-benzyl-idene-amino fragment is planar [with a maximum deviation of 0.056 (3) Å] and forms a dihedral angle of 9.85 (9)° with the central benzene ring. The other fragment is not planar; however, the methoxy-phenol group is planar [with the maximum deviation of 0.033 (2) Å] and makes a dihedral angle of 41.7 (3)° with the central benzene ring. The mol-ecule is stabilized by intra-molecular O-H⋯N hydrogen bonding. The crystal structure is stabilized by weak inter-molecular C-H⋯O hydrogen bonding and C-H⋯π inter-actions.

Related literature

For the biological activity of Schiff bases, see: Aranha et al. (2007 ▶) and for the corrosion inhibition potential of Schiff bases, see: Chetouani et al. (2005 ▶). For related structures, see: Hernández-Molina et al. (1997 ▶); Torayama et al. (1997 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C22H19ClN2O4

M = 410.84

Monoclinic,

a = 9.900 (2) Å

b = 6.8589 (12) Å

c = 28.830 (6) Å

β = 94.659 (4)°

V = 1951.2 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 298 K

0.41 × 0.40 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.912, T max = 0.975

12204 measured reflections

4049 independent reflections

2758 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.131

S = 1.06

4049 reflections

272 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.17 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037386/dn2481sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037386/dn2481Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H19ClN2O4	F(000) = 856
Mr = 410.84	Dx = 1.399 Mg m−3
Monoclinic, P21/n	Melting point = 468.0–470.0 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.900 (2) Å	Cell parameters from 2429 reflections
b = 6.8589 (12) Å	θ = 1.4–26.5°
c = 28.830 (6) Å	µ = 0.23 mm−1
β = 94.659 (4)°	T = 298 K
V = 1951.2 (7) Å3	Block, yellow
Z = 4	0.41 × 0.40 × 0.11 mm

Bruker SMART APEX CCD area-detector diffractometer	4049 independent reflections
Radiation source: fine-focus sealed tube	2758 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 83.66 pixels mm-1	θmax = 26.5°, θmin = 1.4°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −8→7
Tmin = 0.912, Tmax = 0.975	l = −29→36
12204 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0536P)2 + 0.4146P] where P = (Fo2 + 2Fc2)/3
4049 reflections	(Δ/σ)max = 0.002
272 parameters	Δρmax = 0.21 e Å−3
2 restraints	Δρmin = −0.17 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.4334 (2)	0.6076 (3)	1.14002 (7)	0.0751 (5)
O2	0.5923 (2)	0.6402 (2)	1.07204 (7)	0.0671 (5)
O3	0.90619 (18)	−0.3720 (3)	0.77614 (6)	0.0682 (5)
O4	0.86271 (17)	−0.0603 (3)	0.82460 (7)	0.0655 (5)
Cl1	0.83872 (7)	0.86091 (8)	1.00563 (2)	0.0658 (2)
N2	0.9571 (2)	0.2143 (3)	0.87964 (6)	0.0560 (5)
N1	0.71450 (19)	0.4773 (2)	1.00623 (7)	0.0496 (5)
C5	0.8366 (2)	0.3491 (3)	0.94045 (8)	0.0523 (6)
H5	0.7886	0.2325	0.9402	0.063*
C6	0.8069 (2)	0.4937 (3)	0.97170 (8)	0.0470 (5)
C1	0.8754 (2)	0.6715 (3)	0.96890 (8)	0.0497 (6)
C2	0.9714 (3)	0.6982 (3)	0.93761 (8)	0.0594 (7)
H2A	1.0153	0.8177	0.9363	0.071*
C3	1.0032 (3)	0.5503 (4)	0.90814 (8)	0.0602 (7)
H3	1.0695	0.5683	0.8874	0.072*
C4	0.9347 (2)	0.3727 (3)	0.90976 (8)	0.0519 (6)
C7	0.6600 (2)	0.3163 (3)	1.01624 (8)	0.0509 (6)
H7	0.6779	0.2059	0.9990	0.061*
C8	0.5717 (2)	0.2992 (3)	1.05322 (8)	0.0474 (5)
C9	0.5173 (3)	0.1175 (3)	1.06386 (9)	0.0572 (6)
H9	0.5382	0.0082	1.0468	0.069*
C10	0.4341 (3)	0.0992 (3)	1.09897 (10)	0.0633 (7)
H10	0.3987	−0.0222	1.1057	0.076*
C11	0.4019 (2)	0.2612 (4)	1.12488 (9)	0.0590 (6)
H11	0.3432	0.2482	1.1483	0.071*
C12	0.4565 (2)	0.4408 (3)	1.11604 (8)	0.0542 (6)
C13	0.5416 (2)	0.4621 (3)	1.08000 (8)	0.0491 (6)
C15	1.0764 (3)	0.1673 (4)	0.86971 (8)	0.0591 (6)
H15	1.1497	0.2411	0.8819	0.071*
C16	1.1010 (2)	0.0026 (4)	0.84010 (8)	0.0549 (6)
C17	1.2336 (3)	−0.0564 (5)	0.83404 (10)	0.0728 (8)
H17	1.3061	0.0163	0.8473	0.087*
C18	1.2577 (3)	−0.2191 (5)	0.80892 (10)	0.0788 (8)
H18	1.3463	−0.2582	0.8056	0.095*
C19	1.1499 (3)	−0.3269 (4)	0.78828 (9)	0.0687 (7)
H19	1.1673	−0.4366	0.7708	0.082*
C20	1.0186 (2)	−0.2735 (4)	0.79340 (8)	0.0549 (6)
C21	0.9926 (2)	−0.1070 (4)	0.81969 (8)	0.0521 (6)
C14	0.3549 (3)	0.5911 (5)	1.17851 (11)	0.0893 (9)
H14A	0.2687	0.5341	1.1687	0.134*
H14B	0.3412	0.7181	1.1913	0.134*
H14C	0.4013	0.5098	1.2018	0.134*
C22	0.9258 (3)	−0.5492 (4)	0.75161 (11)	0.0839 (9)
H22A	0.9725	−0.5221	0.7244	0.126*
H22B	0.8394	−0.6070	0.7425	0.126*
H22C	0.9787	−0.6377	0.7714	0.126*
H4	0.861 (3)	0.027 (4)	0.8438 (9)	0.102 (12)*
H2	0.643 (3)	0.620 (5)	1.0511 (9)	0.110 (13)*

	U11	U22	U33	U12	U13	U23
O1	0.0940 (14)	0.0583 (11)	0.0763 (12)	0.0002 (9)	0.0263 (11)	−0.0095 (9)
O2	0.0916 (14)	0.0332 (9)	0.0793 (13)	−0.0106 (9)	0.0236 (11)	−0.0061 (8)
O3	0.0633 (11)	0.0731 (12)	0.0684 (11)	−0.0013 (9)	0.0056 (9)	−0.0191 (9)
O4	0.0494 (11)	0.0733 (12)	0.0736 (12)	−0.0005 (9)	0.0040 (9)	−0.0192 (10)
Cl1	0.0819 (5)	0.0395 (3)	0.0753 (4)	−0.0074 (3)	0.0026 (3)	−0.0034 (3)
N2	0.0637 (14)	0.0580 (12)	0.0462 (11)	−0.0071 (10)	0.0044 (10)	−0.0001 (10)
N1	0.0562 (12)	0.0357 (10)	0.0563 (11)	−0.0062 (8)	0.0013 (10)	0.0008 (8)
C5	0.0593 (15)	0.0426 (12)	0.0538 (13)	−0.0104 (11)	−0.0028 (12)	0.0013 (11)
C6	0.0521 (14)	0.0405 (12)	0.0471 (13)	−0.0022 (10)	−0.0045 (11)	0.0041 (10)
C1	0.0610 (15)	0.0372 (12)	0.0490 (13)	−0.0042 (10)	−0.0064 (11)	0.0058 (10)
C2	0.0772 (17)	0.0457 (13)	0.0542 (14)	−0.0173 (12)	−0.0012 (13)	0.0103 (12)
C3	0.0732 (17)	0.0589 (15)	0.0488 (14)	−0.0128 (13)	0.0062 (12)	0.0096 (12)
C4	0.0626 (15)	0.0505 (13)	0.0419 (12)	−0.0081 (11)	−0.0005 (11)	0.0032 (11)
C7	0.0577 (14)	0.0345 (12)	0.0599 (14)	0.0004 (10)	0.0015 (12)	−0.0025 (10)
C8	0.0480 (13)	0.0359 (11)	0.0572 (14)	−0.0027 (9)	−0.0013 (11)	0.0029 (10)
C9	0.0669 (16)	0.0373 (12)	0.0669 (16)	−0.0074 (11)	0.0029 (13)	0.0001 (11)
C10	0.0705 (18)	0.0450 (14)	0.0734 (17)	−0.0167 (12)	−0.0005 (14)	0.0080 (12)
C11	0.0537 (15)	0.0626 (16)	0.0606 (15)	−0.0073 (12)	0.0044 (12)	0.0092 (13)
C12	0.0563 (15)	0.0475 (13)	0.0581 (15)	0.0012 (11)	0.0008 (12)	−0.0016 (12)
C13	0.0527 (14)	0.0352 (12)	0.0586 (14)	−0.0027 (10)	0.0001 (12)	0.0020 (10)
C15	0.0621 (17)	0.0682 (16)	0.0466 (13)	−0.0132 (13)	0.0011 (12)	0.0046 (12)
C16	0.0527 (15)	0.0685 (16)	0.0436 (13)	−0.0057 (12)	0.0045 (11)	0.0049 (12)
C17	0.0521 (17)	0.099 (2)	0.0667 (17)	−0.0091 (15)	0.0034 (14)	−0.0022 (17)
C18	0.0530 (17)	0.108 (2)	0.0767 (19)	0.0087 (16)	0.0120 (15)	−0.0070 (19)
C19	0.0680 (18)	0.0807 (19)	0.0584 (16)	0.0079 (15)	0.0111 (14)	−0.0029 (14)
C20	0.0537 (15)	0.0703 (16)	0.0409 (12)	0.0011 (13)	0.0057 (11)	0.0028 (12)
C21	0.0479 (14)	0.0653 (15)	0.0433 (12)	0.0004 (12)	0.0057 (11)	0.0039 (11)
C14	0.101 (2)	0.092 (2)	0.078 (2)	0.0127 (19)	0.0249 (18)	−0.0081 (17)
C22	0.089 (2)	0.080 (2)	0.082 (2)	0.0068 (17)	−0.0002 (17)	−0.0270 (17)

O1—C12	1.366 (3)	C8—C13	1.403 (3)
O1—C14	1.410 (3)	C9—C10	1.361 (4)
O2—C13	1.348 (3)	C9—H9	0.9300
O2—H2	0.83 (3)	C10—C11	1.390 (4)
O3—C20	1.361 (3)	C10—H10	0.9300
O3—C22	1.427 (3)	C11—C12	1.378 (3)
O4—C21	1.343 (3)	C11—H11	0.9300
O4—H4	0.82 (2)	C12—C13	1.397 (3)
Cl1—C1	1.733 (2)	C15—C16	1.448 (3)
N2—C15	1.279 (3)	C15—H15	0.9300
N2—C4	1.419 (3)	C16—C17	1.398 (4)
N1—C7	1.273 (3)	C16—C21	1.401 (3)
N1—C6	1.410 (3)	C17—C18	1.362 (4)
C5—C4	1.376 (3)	C17—H17	0.9300
C5—C6	1.388 (3)	C18—C19	1.391 (4)
C5—H5	0.9300	C18—H18	0.9300
C6—C1	1.401 (3)	C19—C20	1.370 (4)
C1—C2	1.375 (3)	C19—H19	0.9300
C2—C3	1.377 (3)	C20—C21	1.406 (3)
C2—H2A	0.9300	C14—H14A	0.9600
C3—C4	1.397 (3)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C7—C8	1.438 (3)	C22—H22A	0.9600
C7—H7	0.9300	C22—H22B	0.9600
C8—C9	1.402 (3)	C22—H22C	0.9600
C12—O1—C14	117.2 (2)	O1—C12—C11	124.8 (2)
C13—O2—H2	103 (2)	O1—C12—C13	115.1 (2)
C20—O3—C22	117.6 (2)	C11—C12—C13	120.0 (2)
C21—O4—H4	109 (2)	O2—C13—C12	118.4 (2)
C15—N2—C4	121.5 (2)	O2—C13—C8	122.0 (2)
C7—N1—C6	122.7 (2)	C12—C13—C8	119.6 (2)
C4—C5—C6	122.1 (2)	N2—C15—C16	122.1 (2)
C4—C5—H5	119.0	N2—C15—H15	119.0
C6—C5—H5	119.0	C16—C15—H15	119.0
C5—C6—C1	117.1 (2)	C17—C16—C21	119.2 (2)
C5—C6—N1	125.8 (2)	C17—C16—C15	120.3 (2)
C1—C6—N1	117.1 (2)	C21—C16—C15	120.4 (2)
C2—C1—C6	121.2 (2)	C18—C17—C16	120.7 (3)
C2—C1—Cl1	119.44 (17)	C18—C17—H17	119.7
C6—C1—Cl1	119.39 (19)	C16—C17—H17	119.7
C1—C2—C3	120.8 (2)	C17—C18—C19	120.1 (3)
C1—C2—H2A	119.6	C17—C18—H18	120.0
C3—C2—H2A	119.6	C19—C18—H18	120.0
C2—C3—C4	119.1 (2)	C20—C19—C18	120.9 (3)
C2—C3—H3	120.5	C20—C19—H19	119.6
C4—C3—H3	120.5	C18—C19—H19	119.6
C5—C4—C3	119.6 (2)	O3—C20—C19	125.7 (2)
C5—C4—N2	117.2 (2)	O3—C20—C21	114.8 (2)
C3—C4—N2	123.2 (2)	C19—C20—C21	119.5 (2)
N1—C7—C8	122.2 (2)	O4—C21—C16	122.3 (2)
N1—C7—H7	118.9	O4—C21—C20	118.0 (2)
C8—C7—H7	118.9	C16—C21—C20	119.7 (2)
C9—C8—C13	119.0 (2)	O1—C14—H14A	109.5
C9—C8—C7	120.2 (2)	O1—C14—H14B	109.5
C13—C8—C7	120.8 (2)	H14A—C14—H14B	109.5
C10—C9—C8	120.7 (2)	O1—C14—H14C	109.5
C10—C9—H9	119.6	H14A—C14—H14C	109.5
C8—C9—H9	119.6	H14B—C14—H14C	109.5
C9—C10—C11	120.3 (2)	O3—C22—H22A	109.5
C9—C10—H10	119.8	O3—C22—H22B	109.5
C11—C10—H10	119.8	H22A—C22—H22B	109.5
C12—C11—C10	120.3 (2)	O3—C22—H22C	109.5
C12—C11—H11	119.8	H22A—C22—H22C	109.5
C10—C11—H11	119.8	H22B—C22—H22C	109.5
C4—C5—C6—C1	3.9 (3)	O1—C12—C13—O2	−0.1 (3)
C4—C5—C6—N1	−175.7 (2)	C11—C12—C13—O2	179.4 (2)
C7—N1—C6—C5	9.1 (3)	O1—C12—C13—C8	−179.99 (19)
C7—N1—C6—C1	−170.4 (2)	C11—C12—C13—C8	−0.5 (3)
C5—C6—C1—C2	−2.3 (3)	C9—C8—C13—O2	179.0 (2)
N1—C6—C1—C2	177.3 (2)	C7—C8—C13—O2	0.8 (3)
C5—C6—C1—Cl1	177.84 (16)	C9—C8—C13—C12	−1.1 (3)
N1—C6—C1—Cl1	−2.5 (3)	C7—C8—C13—C12	−179.4 (2)
C6—C1—C2—C3	−0.2 (4)	C4—N2—C15—C16	178.2 (2)
Cl1—C1—C2—C3	179.66 (18)	N2—C15—C16—C17	−173.3 (2)
C1—C2—C3—C4	1.2 (4)	N2—C15—C16—C21	2.5 (4)
C6—C5—C4—C3	−3.0 (3)	C21—C16—C17—C18	−0.5 (4)
C6—C5—C4—N2	179.5 (2)	C15—C16—C17—C18	175.4 (3)
C2—C3—C4—C5	0.3 (4)	C16—C17—C18—C19	1.1 (4)
C2—C3—C4—N2	177.6 (2)	C17—C18—C19—C20	−1.0 (4)
C15—N2—C4—C5	−140.9 (2)	C22—O3—C20—C19	1.8 (4)
C15—N2—C4—C3	41.7 (3)	C22—O3—C20—C21	−176.1 (2)
C6—N1—C7—C8	176.54 (19)	C18—C19—C20—O3	−177.6 (2)
N1—C7—C8—C9	−178.1 (2)	C18—C19—C20—C21	0.3 (4)
N1—C7—C8—C13	0.1 (3)	C17—C16—C21—O4	179.1 (2)
C13—C8—C9—C10	1.4 (3)	C15—C16—C21—O4	3.3 (3)
C7—C8—C9—C10	179.6 (2)	C17—C16—C21—C20	−0.2 (3)
C8—C9—C10—C11	0.0 (4)	C15—C16—C21—C20	−176.1 (2)
C9—C10—C11—C12	−1.6 (4)	O3—C20—C21—O4	−0.9 (3)
C14—O1—C12—C11	4.3 (4)	C19—C20—C21—O4	−179.0 (2)
C14—O1—C12—C13	−176.2 (2)	O3—C20—C21—C16	178.4 (2)
C10—C11—C12—O1	−178.7 (2)	C19—C20—C21—C16	0.3 (3)
C10—C11—C12—C13	1.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.83 (3)	1.81 (3)	2.586 (3)	155 (3)
O4—H4···N2	0.82 (3)	1.86 (3)	2.588 (3)	148 (3)
C11—H11···O4i	0.93	2.59	3.392 (3)	145
C3—H3···Cg3ii	0.93	2.89	3.635 (3)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.83 (3)	1.81 (3)	2.586 (3)	155 (3)
O4—H4⋯N2	0.82 (3)	1.86 (3)	2.588 (3)	148 (3)
C11—H11⋯O4i	0.93	2.59	3.392 (3)	145
C3—H3⋯Cg3ii	0.93	2.89	3.635 (3)	138

Symmetry codes: (i) ; (ii) . Cg3 is the centroid of the C16–C21 ring.