6,6′-Dimeth­oxy-2,2′-[pyridine-2,3-diylbis(nitrilo­methyl­idyne)]diphenol

Li, Q.

doi:10.1107/S160053680905020X

organic compounds

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Volume 66| Part 1| January 2010| Page o70

doi:10.1107/S160053680905020X

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6,6′-Dimethoxy-2,2′-[pyridine-2,3-diylbis(nitrilomethylidyne)]diphenol

Qiuhong Li ^a ^*

^aCollege of Materials Science and Engineering, Shandong University of Technology, Zibo 255049, People's Republic of China
^*Correspondence e-mail: bingxueer79@163.com

(Received 19 November 2009; accepted 22 November 2009; online 9 December 2009)

In the title compound, C₂₁H₁₉N₃O₄, two intramolecular N—H⋯O hydrogen bonds generate two six-membered rings. The dihedral angles between the central heterocyclic ring and the two pendant rings are 61.5 (2) and 63.5 (1)°.

Related literature

For related crystal structures, see: Cimerman et al. (1992 ); Bi et al. (2007 ).

Experimental

Crystal data

C₂₁H₁₉N₃O₄
M_r = 377.39
Monoclinic, P 2₁ /c
a = 6.7006 (9) Å
b = 16.699 (2) Å
c = 17.490 (2) Å
β = 98.772 (2)°
V = 1934.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.21 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.978, T_max = 0.983
9149 measured reflections
3293 independent reflections
1929 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.184
S = 1.04
3293 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.44 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	1.96	2.683 (3)	146
O3—H3⋯N2	0.82	1.85	2.568 (3)	146

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680905020X/hg2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680905020X/hg2604Isup2.hkl

checkCIF report

Comment top

Transition metal complexes with salen-type Schiff-bases as ligands, which has been known as one of the oldest ligands in coordination chemistry, have been intensely studied. Here, we report a new Schiff-base ligand based on 2,3-diaminopyridine and 2-hydroxy-3-methoxybenzaldehyde.

The geometry and labeling scheme for the crystal structure of the title compound are depicted in Figure 1. As can be seen from Figure 1, the title compound affords the potentially tetradentate ligand contributed from the O₂N₂ donor unit. The imide bond lengths are 1.267 (4)Å for N1—C12 and 1.288 (4)Å for N2—C20, respectively, which are basically consistent with the corresponding distances found in other diaminopyridine-based Schiff base ligand (Cimerman, et al., 1992; Bi et al., 2007). There exists relative strong intramolecular O-H···N hydrogen bonding in this compound with the N···O distance 2.683 (3)Å and the bond angle 145.8 ° for O1—N1 and 2.568 (3))Å , 146.1° for O3—N2, respectively; and is similar to its analogues above mentioned.

Related literature top

For related crystal structures, see: Cimerman et al. (1992); Bi et al. (2007).

Experimental top

The title Schiff base ligand was synthesized by condensation 2,3-diaminopyridine and 2-hydroxy-3-methoxybenzaldehyde with the ratio 1:2 in ethanol. Single crystals suitable for X-ray diffraction were obtained after the solvent was partially evaporated.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

Fig. 1. View of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

6,6'-Dimethoxy-2,2'-[pyridine-2,3-diylbis(nitrilomethylidyne)]diphenol top

Crystal data top

C₂₁H₁₉N₃O₄	F(000) = 792
M_r = 377.39	D_x = 1.296 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1473 reflections
a = 6.7006 (9) Å	θ = 2.4–22.1°
b = 16.699 (2) Å	µ = 0.09 mm⁻¹
c = 17.490 (2) Å	T = 293 K
β = 98.772 (2)°	Needle, yellow
V = 1934.2 (5) Å³	0.25 × 0.21 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3293 independent reflections
Radiation source: fine-focus sealed tube	1929 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 24.9°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −7→7
T_min = 0.978, T_max = 0.983	k = −16→19
9149 measured reflections	l = −18→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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.184	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0889P)² + 0.4093P] where P = (F_o² + 2F_c²)/3
3293 reflections	(Δ/σ)_max = 0.001
257 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₂₁H₁₉N₃O₄	V = 1934.2 (5) Å³
M_r = 377.39	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7006 (9) Å	µ = 0.09 mm⁻¹
b = 16.699 (2) Å	T = 293 K
c = 17.490 (2) Å	0.25 × 0.21 × 0.19 mm
β = 98.772 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3293 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1929 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.983	R_int = 0.039
9149 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.184	H-atom parameters constrained
S = 1.04	Δρ_max = 0.40 e Å⁻³
3293 reflections	Δρ_min = −0.44 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
O1	0.0595 (3)	0.84140 (12)	0.30034 (13)	0.0651 (6)
H1	0.0164	0.8097	0.3297	0.098*
O2	0.1593 (4)	0.95259 (14)	0.20681 (15)	0.0796 (8)
O3	0.2804 (3)	0.84262 (13)	0.49519 (12)	0.0597 (6)
H3	0.1757	0.8164	0.4888	0.090*
O4	0.6184 (3)	0.91857 (13)	0.53308 (12)	0.0627 (6)
N1	−0.1950 (4)	0.78816 (15)	0.39342 (14)	0.0500 (6)
N2	0.0306 (4)	0.73504 (13)	0.52610 (15)	0.0521 (6)
N3	−0.4678 (4)	0.69480 (18)	0.41075 (18)	0.0764 (9)
C1	−0.2765 (5)	0.72718 (19)	0.4364 (2)	0.0616 (9)
C2	−0.1580 (5)	0.69766 (19)	0.5039 (2)	0.0609 (9)
C3	−0.2348 (6)	0.63538 (19)	0.5445 (2)	0.0692 (10)
H3A	−0.1586	0.6151	0.5892	0.083*
C4	−0.4230 (5)	0.6040 (2)	0.5184 (2)	0.0695 (10)
H4	−0.4725	0.5626	0.5457	0.083*
C5	−0.5373 (6)	0.6328 (2)	0.4533 (2)	0.0688 (10)
H5	−0.6641	0.6108	0.4369	0.083*
C6	−0.2355 (4)	0.91289 (17)	0.32671 (16)	0.0498 (7)
C7	−0.0614 (4)	0.90562 (17)	0.29041 (16)	0.0484 (7)
C8	−0.0096 (5)	0.96657 (19)	0.24156 (17)	0.0546 (8)
C9	−0.1249 (6)	1.0343 (2)	0.2327 (2)	0.0692 (10)
H9	−0.0909	1.0754	0.2012	0.083*
C10	−0.2936 (6)	1.0428 (2)	0.2704 (2)	0.0818 (11)
H10	−0.3687	1.0899	0.2644	0.098*
C11	−0.3493 (5)	0.9826 (2)	0.3159 (2)	0.0739 (10)
H11	−0.4636	0.9885	0.3397	0.089*
C12	−0.3019 (5)	0.84972 (19)	0.37466 (16)	0.0521 (8)
H12	−0.4259	0.8548	0.3919	0.062*
C13	0.2168 (7)	1.0121 (3)	0.1557 (3)	0.1097 (16)
H13A	0.1166	1.0151	0.1103	0.165*
H13B	0.3447	0.9980	0.1411	0.165*
H13C	0.2279	1.0631	0.1813	0.165*
C14	0.3338 (5)	0.76176 (16)	0.61150 (16)	0.0486 (7)
C15	0.3942 (4)	0.82084 (16)	0.56241 (16)	0.0449 (7)
C16	0.5794 (4)	0.86010 (17)	0.58366 (16)	0.0473 (7)
C17	0.7038 (5)	0.8378 (2)	0.65066 (18)	0.0590 (8)
H17	0.8286	0.8626	0.6639	0.071*
C18	0.6446 (5)	0.7784 (2)	0.69882 (19)	0.0663 (9)
H18	0.7296	0.7642	0.7439	0.080*
C19	0.4630 (6)	0.74141 (19)	0.68010 (19)	0.0642 (9)
H19	0.4237	0.7024	0.7127	0.077*
C20	0.1429 (5)	0.72198 (18)	0.59146 (19)	0.0562 (8)
H20	0.0997	0.6862	0.6263	0.067*
C21	0.8030 (5)	0.9613 (2)	0.5508 (2)	0.0764 (10)
H21A	0.8104	0.9855	0.6010	0.115*
H21B	0.8090	1.0022	0.5127	0.115*
H21C	0.9142	0.9251	0.5508	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0634 (14)	0.0594 (14)	0.0767 (16)	0.0037 (11)	0.0238 (12)	0.0013 (11)
O2	0.0888 (18)	0.0737 (16)	0.0857 (17)	−0.0129 (13)	0.0431 (15)	0.0000 (13)
O3	0.0569 (14)	0.0611 (14)	0.0566 (13)	−0.0124 (10)	−0.0058 (11)	0.0136 (10)
O4	0.0603 (14)	0.0705 (14)	0.0561 (13)	−0.0203 (11)	0.0054 (10)	0.0077 (11)
N1	0.0526 (15)	0.0518 (15)	0.0452 (14)	−0.0090 (12)	0.0067 (12)	−0.0050 (12)
N2	0.0538 (16)	0.0436 (13)	0.0595 (17)	−0.0028 (11)	0.0103 (13)	0.0042 (12)
N3	0.077 (2)	0.075 (2)	0.079 (2)	−0.0199 (16)	0.0192 (17)	−0.0153 (16)
C1	0.064 (2)	0.059 (2)	0.065 (2)	−0.0197 (17)	0.0220 (18)	−0.0158 (17)
C2	0.065 (2)	0.0572 (19)	0.065 (2)	−0.0172 (17)	0.0225 (18)	−0.0119 (17)
C3	0.079 (2)	0.0536 (19)	0.078 (2)	−0.0128 (17)	0.0222 (19)	0.0057 (17)
C4	0.073 (2)	0.064 (2)	0.075 (3)	−0.0230 (19)	0.024 (2)	−0.0108 (19)
C5	0.071 (2)	0.066 (2)	0.073 (2)	−0.0255 (18)	0.021 (2)	−0.0150 (19)
C6	0.0500 (18)	0.0562 (18)	0.0426 (16)	0.0026 (14)	0.0048 (13)	−0.0032 (14)
C7	0.0541 (18)	0.0462 (17)	0.0439 (17)	−0.0047 (14)	0.0048 (14)	−0.0100 (14)
C8	0.0592 (19)	0.0589 (19)	0.0462 (18)	−0.0128 (16)	0.0097 (15)	−0.0099 (15)
C9	0.089 (3)	0.060 (2)	0.056 (2)	−0.0070 (19)	0.0038 (19)	0.0060 (16)
C10	0.086 (3)	0.070 (2)	0.090 (3)	0.019 (2)	0.016 (2)	0.015 (2)
C11	0.070 (2)	0.074 (2)	0.081 (3)	0.0126 (19)	0.0208 (19)	0.005 (2)
C12	0.0511 (18)	0.064 (2)	0.0417 (17)	−0.0053 (16)	0.0087 (14)	−0.0109 (15)
C13	0.138 (4)	0.103 (3)	0.104 (3)	−0.029 (3)	0.070 (3)	0.011 (3)
C14	0.0553 (19)	0.0439 (16)	0.0463 (18)	0.0002 (14)	0.0066 (14)	0.0010 (14)
C15	0.0475 (17)	0.0463 (16)	0.0398 (16)	0.0043 (13)	0.0035 (13)	0.0029 (13)
C16	0.0494 (18)	0.0504 (17)	0.0429 (17)	−0.0016 (14)	0.0092 (14)	−0.0024 (14)
C17	0.0512 (19)	0.070 (2)	0.054 (2)	0.0026 (16)	0.0015 (15)	−0.0093 (16)
C18	0.073 (2)	0.072 (2)	0.0492 (19)	0.0068 (19)	−0.0065 (17)	0.0083 (17)
C19	0.084 (3)	0.0557 (19)	0.051 (2)	0.0035 (18)	0.0050 (18)	0.0115 (16)
C20	0.071 (2)	0.0481 (17)	0.052 (2)	−0.0018 (15)	0.0177 (17)	0.0073 (15)
C21	0.061 (2)	0.080 (2)	0.087 (3)	−0.0251 (19)	0.0094 (19)	0.002 (2)

Geometric parameters (Å, º) top

O1—C7	1.340 (3)	C8—C9	1.366 (5)
O1—H1	0.8200	C9—C10	1.400 (5)
O2—C8	1.383 (4)	C9—H9	0.9300
O2—C13	1.428 (4)	C10—C11	1.369 (5)
O3—C15	1.350 (3)	C10—H10	0.9300
O3—H3	0.8200	C11—H11	0.9300
O4—C16	1.369 (3)	C12—H12	0.9300
O4—C21	1.421 (4)	C13—H13A	0.9600
N1—C12	1.267 (4)	C13—H13B	0.9600
N1—C1	1.423 (4)	C13—H13C	0.9600
N2—C20	1.288 (4)	C14—C15	1.407 (4)
N2—C2	1.410 (4)	C14—C19	1.410 (4)
N3—C5	1.397 (4)	C14—C20	1.436 (4)
N3—C1	1.400 (4)	C15—C16	1.402 (4)
C1—C2	1.408 (5)	C16—C17	1.382 (4)
C2—C3	1.401 (4)	C17—C18	1.397 (4)
C3—C4	1.377 (5)	C17—H17	0.9300
C3—H3A	0.9300	C18—C19	1.360 (5)
C4—C5	1.359 (5)	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C5—H5	0.9300	C20—H20	0.9300
C6—C11	1.389 (4)	C21—H21A	0.9600
C6—C7	1.416 (4)	C21—H21B	0.9600
C6—C12	1.459 (4)	C21—H21C	0.9600
C7—C8	1.406 (4)

C7—O1—H1	109.5	C10—C11—H11	120.0
C8—O2—C13	118.3 (3)	C6—C11—H11	120.0
C15—O3—H3	109.5	N1—C12—C6	121.7 (3)
C16—O4—C21	117.5 (2)	N1—C12—H12	119.1
C12—N1—C1	118.0 (3)	C6—C12—H12	119.1
C20—N2—C2	123.2 (3)	O2—C13—H13A	109.5
C5—N3—C1	118.6 (3)	O2—C13—H13B	109.5
N3—C1—C2	120.3 (3)	H13A—C13—H13B	109.5
N3—C1—N1	120.9 (3)	O2—C13—H13C	109.5
C2—C1—N1	118.7 (3)	H13A—C13—H13C	109.5
C3—C2—C1	118.8 (3)	H13B—C13—H13C	109.5
C3—C2—N2	124.9 (3)	C15—C14—C19	119.5 (3)
C1—C2—N2	116.3 (3)	C15—C14—C20	120.3 (3)
C4—C3—C2	120.2 (4)	C19—C14—C20	120.3 (3)
C4—C3—H3A	119.9	O3—C15—C16	117.7 (2)
C2—C3—H3A	119.9	O3—C15—C14	122.9 (3)
C5—C4—C3	120.9 (3)	C16—C15—C14	119.4 (3)
C5—C4—H4	119.5	O4—C16—C17	126.2 (3)
C3—C4—H4	119.5	O4—C16—C15	114.2 (2)
C4—C5—N3	121.1 (3)	C17—C16—C15	119.6 (3)
C4—C5—H5	119.4	C16—C17—C18	120.8 (3)
N3—C5—H5	119.4	C16—C17—H17	119.6
C11—C6—C7	118.9 (3)	C18—C17—H17	119.6
C11—C6—C12	118.4 (3)	C19—C18—C17	120.3 (3)
C7—C6—C12	122.7 (3)	C19—C18—H18	119.9
O1—C7—C8	117.2 (3)	C17—C18—H18	119.9
O1—C7—C6	122.3 (3)	C18—C19—C14	120.4 (3)
C8—C7—C6	120.5 (3)	C18—C19—H19	119.8
C9—C8—O2	125.2 (3)	C14—C19—H19	119.8
C9—C8—C7	118.7 (3)	N2—C20—C14	121.1 (3)
O2—C8—C7	116.1 (3)	N2—C20—H20	119.5
C8—C9—C10	120.9 (3)	C14—C20—H20	119.5
C8—C9—H9	119.5	O4—C21—H21A	109.5
C10—C9—H9	119.5	O4—C21—H21B	109.5
C11—C10—C9	120.7 (3)	H21A—C21—H21B	109.5
C11—C10—H10	119.6	O4—C21—H21C	109.5
C9—C10—H10	119.6	H21A—C21—H21C	109.5
C10—C11—C6	120.1 (3)	H21B—C21—H21C	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	1.96	2.683 (3)	146
O3—H3···N2	0.82	1.85	2.568 (3)	146

Experimental details

Crystal data
Chemical formula	C₂₁H₁₉N₃O₄
M_r	377.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.7006 (9), 16.699 (2), 17.490 (2)
β (°)	98.772 (2)
V (Å³)	1934.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.21 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.978, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	9149, 3293, 1929
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.591

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.184, 1.04
No. of reflections	3293
No. of parameters	257
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.44

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.96	2.683 (3)	145.8
O3—H3···N2	0.82	1.85	2.568 (3)	146.1

References

Bi, W.-Y., Lü, X.-Q., Cai, W.-L., Song, J.-R. & Ng, S. W. (2007). Acta Cryst. E63, o1615–o1616. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 66| Part 1| January 2010| Page o70

doi:10.1107/S160053680905020X

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