(E,E)-6,6′-Dimeth­oxy-2,2′-[o-phenyl­ene­bis(nitrilo­methyl­idyne)]diphenol

Wang, Y.; Li, H.-G.; Yin, H.; Wei, G.-D.; Wang, X.

doi:10.1107/S1600536809008757

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o754

doi:10.1107/S1600536809008757

Open

access

(E,E)-6,6′-Dimethoxy-2,2′-[o-phenylenebis(nitrilomethylidyne)]diphenol

Yong Wang,^a ^* Hong-Gang Li,^b Handong Yin,^a Guo-Dong Wei ^c and Xiao Wang ^a

^aDepartment of Chemistry, Liaocheng University, Liaocheng 252059, People's Republic of China, ^bClinical Medicine Department, Weifang Medical University, Shangdong 261042, People's Republic of China, and ^cShandong Donge Experimental High School, Shandong 252200, People's Republic of China
^*Correspondence e-mail: yongwang@lcu.edu.cn

(Received 13 February 2009; accepted 10 March 2009; online 14 March 2009)

In the title compound, C₂₂H₂₀N₂O₄, the central benzene ring forms dihedral angles of 3.2 (2) and 61.1 (1)° with the two outer substituted benzene rings. Intramolecular O—H⋯N hydrogen bonds are formed by both hydroxyl groups.

Related literature

For background literature concerning salen-type ligands, see: Zhang et al. (1990 ). For related structures, see: Lo et al. (2006 ).

Experimental

Crystal data

C₂₂H₂₀N₂O₄
M_r = 376.40
Monoclinic, P 2₁ /c
a = 6.5863 (8) Å
b = 16.726 (2) Å
c = 17.023 (3) Å
β = 97.926 (2)°
V = 1857.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.33 × 0.15 × 0.09 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 0.992
9269 measured reflections
3263 independent reflections
1217 reflections with I > 2σ(I)
R_int = 0.098

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.128
S = 0.82
3263 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.88	2.605 (4)	146
O3—H3⋯N2	0.82	1.82	2.542 (3)	146

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008757/bi2352sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008757/bi2352Isup2.hkl

checkCIF report

Comment top

Salen-type ligands are amongst the oldest ligands in coordination chemistry and have received considerable interest since Jacobsen and Katsuki first reported their significant success using chiral manganese(III) salen Schiff-base catalysts in the asymmetric epoxidation of unfunctionalized olefins (Zhang, et al., 1990).

The title compound (Fig. 1) was obtained by reaction of o-phenylenediamine and 2-hydroxy-3-methoxybenzaldehyde. The bond lengths and angles are comparable to those in the related compound N,N'-bis(3- methoxysalicylidene)phenylene-1,2-diamine (Lo et al., 2006). The central benzene ring is almost coplanar with the benzene ring C16–C21; the dihedral angle between the two planes is 3.21 (22) °. However, the dihedral angle of the central benzene ring and the benzene ring C8–C13 is 61.13 (11)°. Intramolecular O—H···N hydrogen bonds are formed by both hydroxyl groups (Table 1).

Related literature top

For background literature concerning salen-type ligands, see: Zhang et al. (1990). For related structures, see: Lo et al. (2006).

Experimental top

To a solution of o-phenylenediamine (3 mmol) in ethanol (30 ml) was added 2-hydroxy-3-methoxybenzaldehyde (6 mmol). The mixture was refluxed with stirring for 20 min and an orange precipitate was obtained. Orange crystals suitable for X-ray diffraction analysis formed after several weeks on slow evaporation of an ethanol solution at room temperature. Elemental analysis: calculated for C₂₂H₂₀N₂O₄: C 70.20, H 5.36, N 7.44%; found: C 70.28, H 5.32, N 7.49%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound showing 30% probability displacement ellipsoids for non-H atoms.

(E,E)-6,6'-Dimethoxy-2,2'-[o- phenylenebis(nitrilomethylidyne)]diphenol top

Crystal data top

C₂₂H₂₀N₂O₄	F(000) = 792
M_r = 376.40	D_x = 1.346 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 802 reflections
a = 6.5863 (8) Å	θ = 2.4–25.3°
b = 16.726 (2) Å	µ = 0.09 mm⁻¹
c = 17.023 (3) Å	T = 298 K
β = 97.926 (2)°	Block, orange
V = 1857.3 (4) Å³	0.33 × 0.15 × 0.09 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	3263 independent reflections
Radiation source: fine-focus sealed tube	1217 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.098
ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.970, T_max = 0.992	k = −19→19
9269 measured reflections	l = −10→20

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 0.82	w = 1/[σ²(F_o²) + (0.0396P)²] where P = (F_o² + 2F_c²)/3
3263 reflections	(Δ/σ)_max < 0.001
257 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₂H₂₀N₂O₄	V = 1857.3 (4) Å³
M_r = 376.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.5863 (8) Å	µ = 0.09 mm⁻¹
b = 16.726 (2) Å	T = 298 K
c = 17.023 (3) Å	0.33 × 0.15 × 0.09 mm
β = 97.926 (2)°

Data collection top

Siemens SMART CCD diffractometer	3263 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1217 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.992	R_int = 0.098
9269 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 0.82	Δρ_max = 0.15 e Å⁻³
3263 reflections	Δρ_min = −0.16 e Å⁻³
257 parameters

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	U_iso*/U_eq
N1	−0.1935 (4)	0.21173 (18)	0.39296 (16)	0.0568 (8)
N2	0.0295 (4)	0.26464 (15)	0.52584 (18)	0.0579 (8)
O1	0.0593 (4)	0.15813 (15)	0.30030 (15)	0.0719 (7)
H1	0.0140	0.1899	0.3303	0.108*
O2	0.1592 (4)	0.04788 (15)	0.20699 (16)	0.0868 (9)
O3	0.2802 (3)	0.15729 (14)	0.49515 (14)	0.0676 (7)
H3	0.1719	0.1822	0.4903	0.101*
O4	0.6184 (3)	0.08108 (14)	0.53290 (13)	0.0698 (7)
C1	−0.2767 (6)	0.2731 (2)	0.4365 (2)	0.0575 (10)
C2	−0.1578 (6)	0.3022 (2)	0.5035 (2)	0.0572 (10)
C3	−0.2322 (6)	0.3642 (2)	0.5450 (2)	0.0715 (11)
H3A	−0.1540	0.3843	0.5903	0.086*
C4	−0.4199 (7)	0.3955 (2)	0.5195 (3)	0.0834 (13)
H4	−0.4689	0.4374	0.5475	0.100*
C5	−0.5373 (6)	0.3668 (3)	0.4537 (3)	0.0797 (13)
H5	−0.6659	0.3887	0.4371	0.096*
C6	−0.4654 (6)	0.3057 (2)	0.4120 (2)	0.0719 (11)
H6	−0.5451	0.2862	0.3667	0.086*
C7	−0.3021 (5)	0.1499 (2)	0.37462 (19)	0.0581 (10)
H7	−0.4285	0.1452	0.3928	0.070*
C8	−0.2348 (5)	0.0871 (2)	0.3265 (2)	0.0555 (9)
C9	−0.0623 (6)	0.0944 (2)	0.2904 (2)	0.0552 (9)
C10	−0.0088 (6)	0.0337 (2)	0.2413 (2)	0.0590 (10)
C11	−0.1242 (7)	−0.0340 (2)	0.2324 (2)	0.0754 (12)
H11	−0.0887	−0.0749	0.1998	0.090*
C12	−0.2921 (7)	−0.0425 (3)	0.2709 (3)	0.0910 (14)
H12	−0.3674	−0.0897	0.2656	0.109*
C13	−0.3491 (6)	0.0175 (3)	0.3167 (2)	0.0819 (12)
H13	−0.4654	0.0119	0.3416	0.098*
C14	0.2181 (7)	−0.0106 (2)	0.1550 (3)	0.1190 (17)
H14A	0.2234	−0.0619	0.1805	0.178*
H14B	0.3510	0.0023	0.1414	0.178*
H14C	0.1202	−0.0121	0.1077	0.178*
C15	0.1427 (6)	0.27815 (19)	0.5911 (2)	0.0595 (10)
H15	0.1003	0.3152	0.6262	0.071*
C16	0.3323 (5)	0.23818 (19)	0.6117 (2)	0.0522 (9)
C17	0.3958 (5)	0.1790 (2)	0.5627 (2)	0.0516 (9)
C18	0.5797 (5)	0.1401 (2)	0.5837 (2)	0.0543 (9)
C19	0.7041 (5)	0.1621 (2)	0.6500 (2)	0.0668 (11)
H19	0.8303	0.1371	0.6631	0.080*
C20	0.6450 (7)	0.2217 (2)	0.6987 (2)	0.0743 (12)
H20	0.7314	0.2364	0.7443	0.089*
C21	0.4615 (6)	0.2584 (2)	0.6800 (2)	0.0709 (11)
H21	0.4218	0.2977	0.7134	0.085*
C22	0.8046 (5)	0.0386 (2)	0.5504 (2)	0.0837 (13)
H22A	0.9176	0.0751	0.5522	0.125*
H22B	0.8139	−0.0008	0.5100	0.125*
H22C	0.8088	0.0126	0.6009	0.125*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.064 (2)	0.059 (2)	0.0483 (18)	0.0109 (17)	0.0112 (15)	0.0045 (17)
N2	0.059 (2)	0.0576 (19)	0.057 (2)	0.0020 (16)	0.0072 (16)	−0.0030 (17)
O1	0.0748 (18)	0.0689 (18)	0.076 (2)	−0.0043 (14)	0.0235 (13)	−0.0008 (15)
O2	0.096 (2)	0.085 (2)	0.089 (2)	0.0161 (16)	0.0462 (17)	0.0009 (17)
O3	0.0697 (18)	0.0699 (17)	0.0598 (16)	0.0129 (13)	−0.0036 (13)	−0.0172 (14)
O4	0.0727 (18)	0.0755 (17)	0.0601 (16)	0.0191 (14)	0.0055 (13)	−0.0091 (15)
C1	0.067 (3)	0.054 (2)	0.054 (3)	0.009 (2)	0.020 (2)	0.016 (2)
C2	0.066 (3)	0.050 (2)	0.059 (3)	0.005 (2)	0.019 (2)	0.006 (2)
C3	0.076 (3)	0.063 (3)	0.077 (3)	0.012 (2)	0.017 (2)	−0.005 (2)
C4	0.106 (4)	0.069 (3)	0.081 (3)	0.029 (3)	0.035 (3)	0.006 (3)
C5	0.081 (3)	0.079 (3)	0.083 (3)	0.035 (3)	0.027 (3)	0.025 (3)
C6	0.077 (3)	0.080 (3)	0.059 (3)	0.024 (2)	0.013 (2)	0.015 (2)
C7	0.060 (2)	0.068 (3)	0.047 (2)	0.007 (2)	0.0104 (18)	0.010 (2)
C8	0.054 (2)	0.062 (3)	0.052 (2)	0.001 (2)	0.0114 (19)	0.008 (2)
C9	0.062 (3)	0.052 (2)	0.050 (2)	0.002 (2)	0.0035 (19)	0.007 (2)
C10	0.072 (3)	0.061 (3)	0.045 (2)	0.009 (2)	0.013 (2)	0.011 (2)
C11	0.094 (3)	0.071 (3)	0.060 (3)	0.007 (3)	0.007 (2)	−0.004 (2)
C12	0.103 (4)	0.076 (3)	0.096 (4)	−0.021 (3)	0.021 (3)	−0.015 (3)
C13	0.077 (3)	0.085 (3)	0.089 (3)	−0.018 (3)	0.027 (2)	−0.006 (3)
C14	0.157 (4)	0.110 (4)	0.106 (4)	0.039 (3)	0.073 (3)	−0.011 (3)
C15	0.076 (3)	0.048 (2)	0.058 (3)	0.002 (2)	0.020 (2)	−0.004 (2)
C16	0.061 (2)	0.044 (2)	0.053 (2)	−0.0026 (18)	0.0124 (19)	−0.0024 (19)
C17	0.058 (2)	0.053 (2)	0.043 (2)	−0.0057 (19)	0.0038 (18)	0.0003 (19)
C18	0.059 (2)	0.058 (2)	0.045 (2)	0.005 (2)	0.0057 (19)	0.001 (2)
C19	0.064 (3)	0.078 (3)	0.058 (3)	0.003 (2)	0.007 (2)	0.008 (2)
C20	0.088 (3)	0.079 (3)	0.052 (3)	−0.009 (2)	−0.002 (2)	−0.007 (2)
C21	0.088 (3)	0.068 (3)	0.055 (3)	−0.001 (2)	0.002 (2)	−0.015 (2)
C22	0.075 (3)	0.090 (3)	0.086 (3)	0.034 (2)	0.013 (2)	−0.002 (3)

Geometric parameters (Å, º) top

N1—C7	1.272 (4)	C8—C13	1.383 (4)
N1—C1	1.419 (4)	C9—C10	1.391 (4)
N2—C15	1.270 (4)	C10—C11	1.360 (5)
N2—C2	1.389 (4)	C11—C12	1.368 (5)
O1—C9	1.330 (4)	C11—H11	0.930
O1—H1	0.820	C12—C13	1.357 (5)
O2—C10	1.342 (4)	C12—H12	0.930
O2—C14	1.409 (4)	C13—H13	0.930
O3—C17	1.339 (3)	C14—H14A	0.960
O3—H3	0.820	C14—H14B	0.960
O4—C18	1.360 (4)	C14—H14C	0.960
O4—C22	1.413 (3)	C15—C16	1.417 (4)
C1—C6	1.370 (4)	C15—H15	0.930
C1—C2	1.381 (4)	C16—C21	1.385 (4)
C2—C3	1.381 (4)	C16—C17	1.395 (4)
C3—C4	1.358 (4)	C17—C18	1.377 (4)
C3—H3A	0.930	C18—C19	1.351 (4)
C4—C5	1.358 (5)	C19—C20	1.385 (4)
C4—H4	0.930	C19—H19	0.930
C5—C6	1.365 (5)	C20—C21	1.354 (4)
C5—H5	0.930	C20—H20	0.930
C6—H6	0.930	C21—H21	0.930
C7—C8	1.439 (4)	C22—H22A	0.960
C7—H7	0.930	C22—H22B	0.960
C8—C9	1.370 (4)	C22—H22C	0.960

C7—N1—C1	118.1 (3)	C13—C12—C11	120.3 (4)
C15—N2—C2	123.4 (3)	C13—C12—H12	119.8
C9—O1—H1	109.5	C11—C12—H12	119.8
C10—O2—C14	117.7 (3)	C12—C13—C8	120.2 (4)
C17—O3—H3	109.5	C12—C13—H13	119.9
C18—O4—C22	117.7 (3)	C8—C13—H13	119.9
C6—C1—C2	119.9 (4)	O2—C14—H14A	109.5
C6—C1—N1	121.9 (4)	O2—C14—H14B	109.5
C2—C1—N1	118.1 (3)	H14A—C14—H14B	109.5
C1—C2—C3	119.1 (4)	O2—C14—H14C	109.5
C1—C2—N2	116.6 (3)	H14A—C14—H14C	109.5
C3—C2—N2	124.3 (4)	H14B—C14—H14C	109.5
C4—C3—C2	119.9 (4)	N2—C15—C16	121.6 (3)
C4—C3—H3A	120.1	N2—C15—H15	119.2
C2—C3—H3A	120.1	C16—C15—H15	119.2
C5—C4—C3	121.1 (4)	C21—C16—C17	118.3 (3)
C5—C4—H4	119.4	C21—C16—C15	120.8 (4)
C3—C4—H4	119.4	C17—C16—C15	120.9 (3)
C4—C5—C6	119.7 (4)	O3—C17—C18	118.1 (3)
C4—C5—H5	120.2	O3—C17—C16	121.6 (3)
C6—C5—H5	120.2	C18—C17—C16	120.4 (3)
C5—C6—C1	120.4 (4)	C19—C18—O4	125.7 (3)
C5—C6—H6	119.8	C19—C18—C17	119.9 (4)
C1—C6—H6	119.8	O4—C18—C17	114.4 (3)
N1—C7—C8	121.8 (4)	C18—C19—C20	120.5 (4)
N1—C7—H7	119.1	C18—C19—H19	119.8
C8—C7—H7	119.1	C20—C19—H19	119.8
C9—C8—C13	119.5 (4)	C21—C20—C19	120.1 (3)
C9—C8—C7	122.0 (4)	C21—C20—H20	120.0
C13—C8—C7	118.5 (4)	C19—C20—H20	120.0
O1—C9—C8	122.5 (4)	C20—C21—C16	120.8 (4)
O1—C9—C10	117.6 (4)	C20—C21—H21	119.6
C8—C9—C10	119.9 (4)	C16—C21—H21	119.6
O2—C10—C11	125.5 (4)	O4—C22—H22A	109.5
O2—C10—C9	115.1 (4)	O4—C22—H22B	109.5
C11—C10—C9	119.4 (4)	H22A—C22—H22B	109.5
C10—C11—C12	120.6 (4)	O4—C22—H22C	109.5
C10—C11—H11	119.7	H22A—C22—H22C	109.5
C12—C11—H11	119.7	H22B—C22—H22C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.88	2.605 (4)	146
O3—H3···N2	0.82	1.82	2.542 (3)	146

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀N₂O₄
M_r	376.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.5863 (8), 16.726 (2), 17.023 (3)
β (°)	97.926 (2)
V (Å³)	1857.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.15 × 0.09

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	9269, 3263, 1217
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.128, 0.82
No. of reflections	3263
No. of parameters	257
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.88	2.605 (4)	146.4
O3—H3···N2	0.82	1.82	2.542 (3)	146.4

Acknowledgements

The authors acknowledge the support of the National Natural Science Foundation of Liaocheng University (No. X051040).

References

Lo, W.-K., Wong, W.-K., Wong, W.-Y., Guo, J. P., Yeung, K.-T., Cheng, Y.-K., Yang, X. P. & Jones, R. A. (2006). Inorg. Chem. 45, 9315–9325. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Zhang, W., Loebach, J. L., Wilson, S. R. & Jacobsen, E. N. (1990). J. Am. Chem. Soc. 112, 2801–2804. CSD CrossRef CAS Web of Science Google Scholar