1,1′-[(1E,11E)-5,8-Dioxa-2,11-diazo­nia­dodeca-1,11-diene-1,12-di­yl]dinaph­thal­en-2-olate

Abstract

The title compound, C₂₈H₂₈N₂O₄, crystallizes in a zwitterionic form with deprotonated naphthol hy­droxy groups and protonated imine N atoms. The asymmetric unit contains one half-mol­ecule located on a twofold rotation axis. Intra­molecular N—H⋯O hydrogen bonds occur and the two bicyclic ring systems form a dihedral angle of 64.2 (1)°. In the crystal, weak inter­molecular C—H⋯O hydrogen bonds link the mol­ecules into layers parallel to the bc plane.

Related literature

For applications of Schiff bases in coordination chemistry, see: Osowle (2008 ▶). For related structures, see: Etemadi et al. (2004 ▶); Liu et al. (2010 ▶); Farag et al. (2010 ▶; 2011 ▶).

Experimental

Crystal data

• C₂₈H₂₈N₂O₄

• M _r = 456.52

• Orthorhombic,

• a = 44.704 (4) Å

• b = 6.3576 (6) Å

• c = 8.2074 (9) Å

• V = 2332.6 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 298 K

• 0.50 × 0.37 × 0.11 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.958, T _max = 0.991

• 9099 measured reflections

• 2060 independent reflections

• 1162 reflections with I > 2σ(I)

• R _int = 0.081

Refinement

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 0.224

• S = 1.00

• 2060 reflections

• 155 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86	1.85	2.542 (5)	136
C14—H14B⋯O2i	0.97	2.58	3.382 (5)	141
C12—H12B⋯O1ii	0.97	2.50	3.257 (5)	134

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Schiff bases have various applications in coordination chemistry (Osowle, 2008). Herewith we present the title compound (I), which is a new crowned Schiff base.

In (I) (Fig. 1), all bond lengths and angles are usual and comparable with those observed in the related compounds (Etemadi et al., 2004; Liu et al., 2010; Farag et al., 2010, 2011). Each molecule is situated on a twofold rotational axis. Intramolecular N—H···O hydrogen bonds (Table 1) influence the molecular conformation - two bicycles form a dihedral angle of 64.2 (1)°. In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) link molecules into layers parallel to bc plane.

Experimental

The title compound was synthesized by adding drop-wise a solution of 3,6-dioxa-1,8-diaminooctane (1.48 g,10 mmol) in absolute methanol (10 mL) to a methanol solution (20 mL) of 2-hydroxy-1-naphthaldehyde (3.4438 g,20 mmol) under stirring at room temperature. The resultant reaction mixture was then refluxed for 5 h, cooled and concentrated under reduced pressure, and then the residue was retained at -268 K for overnight. The bright yellow crystal which suitable for X-ray analysis was formed, filtered and dried under reduced pressure.Yield:82%. Analysis found: C 73.07, H 6.06, N 6.51%; calculated for C₂₈H₂₈N₂O₄ (Mr=456.54): C 73.66, H 6.18, N 6.14%.

Refinement

C-bound H atoms were geometrically positioned [C—H 0.93–0.97 Å]. Atom H1A was located on a difference map, but placed in idealized position [N—H 0.86 Å]. All H atoms were refined as riding atoms, with U_iso(H) = 1.2–1.5 U_iso of the parent atom.

Figures

Fig. 1.

The molecular structure of (I) showing the atomic labels and 30% probability displacement ellipsoids. Symmetry code: (A) -x + 1/2,-y + 1,z.

Crystal data

C28H28N2O4	F(000) = 968
Mr = 456.52	Dx = 1.300 Mg m−3
Orthorhombic, Pcca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ac	Cell parameters from 1398 reflections
a = 44.704 (4) Å	θ = 2.7–22.6°
b = 6.3576 (6) Å	µ = 0.09 mm−1
c = 8.2074 (9) Å	T = 298 K
V = 2332.6 (4) Å3	Block, yellow
Z = 4	0.50 × 0.37 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2060 independent reflections
Radiation source: fine-focus sealed tube	1162 reflections with I > 2σ(I)
graphite	Rint = 0.081
phi and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −53→28
Tmin = 0.958, Tmax = 0.991	k = −7→7
9099 measured reflections	l = −9→9

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068	H-atom parameters constrained
wR(F2) = 0.224	w = 1/[σ2(Fo2) + (0.088P)2 + 3.8548P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2060 reflections	Δρmax = 0.21 e Å−3
155 parameters	Δρmin = −0.19 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0055 (16)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.16369 (7)	0.4462 (5)	0.0795 (4)	0.0479 (10)
H1A	0.1720	0.5537	0.1239	0.058*
C2	0.11853 (8)	0.6454 (6)	0.0728 (5)	0.0370 (9)
O1	0.15974 (7)	0.8123 (5)	0.2021 (4)	0.0628 (10)
O2	0.22075 (6)	0.4082 (5)	0.2116 (4)	0.0541 (9)
C11	0.08741 (8)	0.6581 (6)	0.0253 (5)	0.0388 (10)
C1	0.13580 (8)	0.4646 (6)	0.0400 (5)	0.0402 (10)
H1	0.1266	0.3525	−0.0129	0.048*
C6	0.07056 (9)	0.8373 (6)	0.0703 (5)	0.0464 (11)
C3	0.13216 (10)	0.8124 (6)	0.1618 (5)	0.0463 (11)
C10	0.07267 (8)	0.5045 (7)	−0.0672 (5)	0.0469 (11)
H10	0.0832	0.3861	−0.1007	0.056*
C12	0.18209 (9)	0.2620 (7)	0.0560 (6)	0.0505 (12)
H12A	0.1941	0.2793	−0.0415	0.061*
H12B	0.1694	0.1397	0.0410	0.061*
C4	0.11373 (10)	0.9880 (7)	0.2060 (6)	0.0557 (12)
H4	0.1220	1.0978	0.2657	0.067*
C5	0.08502 (10)	0.9976 (7)	0.1636 (5)	0.0550 (12)
H5	0.0739	1.1138	0.1962	0.066*
C8	0.02674 (10)	0.6990 (9)	−0.0632 (6)	0.0650 (14)
H8	0.0067	0.7120	−0.0922	0.078*
C7	0.04054 (10)	0.8504 (8)	0.0252 (6)	0.0572 (13)
H7	0.0296	0.9677	0.0571	0.069*
C9	0.04327 (9)	0.5238 (8)	−0.1096 (6)	0.0553 (12)
H9	0.0342	0.4182	−0.1703	0.066*
C13	0.20210 (9)	0.2282 (7)	0.1994 (6)	0.0566 (13)
H13A	0.1903	0.2115	0.2979	0.068*
H13B	0.2141	0.1027	0.1840	0.068*
C14	0.24105 (8)	0.4015 (7)	0.3430 (5)	0.0507 (12)
H14A	0.2542	0.2808	0.3319	0.061*
H14B	0.2302	0.3884	0.4449	0.061*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0378 (17)	0.048 (2)	0.059 (2)	−0.0032 (15)	−0.0074 (17)	0.0003 (19)
C2	0.041 (2)	0.035 (2)	0.035 (2)	−0.0033 (17)	−0.0019 (18)	0.0031 (18)
O1	0.066 (2)	0.0485 (19)	0.074 (2)	−0.0125 (15)	−0.0256 (18)	0.0002 (17)
O2	0.0413 (15)	0.064 (2)	0.057 (2)	−0.0092 (14)	−0.0097 (14)	0.0128 (16)
C11	0.042 (2)	0.042 (2)	0.032 (2)	0.0007 (18)	0.0030 (18)	0.0051 (19)
C1	0.039 (2)	0.042 (2)	0.040 (2)	−0.0059 (17)	−0.0017 (19)	0.0059 (19)
C6	0.054 (2)	0.043 (2)	0.043 (3)	0.000 (2)	0.007 (2)	0.004 (2)
C3	0.059 (3)	0.037 (2)	0.043 (3)	−0.006 (2)	−0.005 (2)	0.004 (2)
C10	0.043 (2)	0.050 (2)	0.049 (3)	−0.003 (2)	−0.004 (2)	−0.003 (2)
C12	0.040 (2)	0.054 (3)	0.057 (3)	0.000 (2)	−0.003 (2)	−0.003 (2)
C4	0.081 (3)	0.041 (2)	0.046 (3)	−0.011 (3)	−0.004 (3)	−0.002 (2)
C5	0.074 (3)	0.043 (3)	0.049 (3)	0.006 (2)	0.006 (2)	0.001 (2)
C8	0.040 (2)	0.091 (4)	0.064 (3)	0.005 (3)	−0.001 (2)	0.001 (3)
C7	0.052 (3)	0.061 (3)	0.059 (3)	0.017 (2)	0.008 (2)	0.005 (3)
C9	0.045 (2)	0.068 (3)	0.053 (3)	−0.001 (2)	−0.006 (2)	−0.005 (3)
C13	0.047 (2)	0.054 (3)	0.069 (3)	0.000 (2)	−0.011 (2)	0.004 (3)
C14	0.044 (2)	0.067 (3)	0.042 (3)	0.004 (2)	−0.003 (2)	0.005 (2)

Geometric parameters (Å, °)

N1—C1	1.294 (4)	C12—C13	1.494 (6)
N1—C12	1.444 (5)	C12—H12A	0.9700
N1—H1A	0.8600	C12—H12B	0.9700
C2—C1	1.410 (5)	C4—C5	1.331 (6)
C2—C3	1.426 (5)	C4—H4	0.9300
C2—C11	1.447 (5)	C5—H5	0.9300
O1—C3	1.276 (5)	C8—C7	1.354 (7)
O2—C14	1.410 (5)	C8—C9	1.390 (6)
O2—C13	1.420 (5)	C8—H8	0.9300
C11—C10	1.402 (5)	C7—H7	0.9300
C11—C6	1.415 (5)	C9—H9	0.9300
C1—H1	0.9300	C13—H13A	0.9700
C6—C7	1.394 (6)	C13—H13B	0.9700
C6—C5	1.429 (6)	C14—C14i	1.486 (8)
C3—C4	1.434 (6)	C14—H14A	0.9700
C10—C9	1.365 (5)	C14—H14B	0.9700
C10—H10	0.9300
C1—N1—C12	126.1 (4)	C5—C4—C3	121.6 (4)
C1—N1—H1A	117.0	C5—C4—H4	119.2
C12—N1—H1A	117.0	C3—C4—H4	119.2
C1—C2—C3	118.1 (3)	C4—C5—C6	122.9 (4)
C1—C2—C11	121.4 (3)	C4—C5—H5	118.6
C3—C2—C11	120.5 (4)	C6—C5—H5	118.6
C14—O2—C13	114.1 (3)	C7—C8—C9	118.3 (4)
C10—C11—C6	116.9 (4)	C7—C8—H8	120.8
C10—C11—C2	124.0 (4)	C9—C8—H8	120.8
C6—C11—C2	119.1 (4)	C8—C7—C6	122.6 (4)
N1—C1—C2	123.6 (4)	C8—C7—H7	118.7
N1—C1—H1	118.2	C6—C7—H7	118.7
C2—C1—H1	118.2	C10—C9—C8	120.9 (5)
C7—C6—C11	119.4 (4)	C10—C9—H9	119.5
C7—C6—C5	122.3 (4)	C8—C9—H9	119.5
C11—C6—C5	118.2 (4)	O2—C13—C12	106.9 (4)
O1—C3—C2	123.1 (4)	O2—C13—H13A	110.3
O1—C3—C4	119.3 (4)	C12—C13—H13A	110.3
C2—C3—C4	117.6 (4)	O2—C13—H13B	110.3
C9—C10—C11	121.9 (4)	C12—C13—H13B	110.3
C9—C10—H10	119.1	H13A—C13—H13B	108.6
C11—C10—H10	119.1	O2—C14—C14i	108.7 (3)
N1—C12—C13	110.7 (4)	O2—C14—H14A	109.9
N1—C12—H12A	109.5	C14i—C14—H14A	109.9
C13—C12—H12A	109.5	O2—C14—H14B	109.9
N1—C12—H12B	109.5	C14i—C14—H14B	109.9
C13—C12—H12B	109.5	H14A—C14—H14B	108.3
H12A—C12—H12B	108.1
C1—C2—C11—C10	−5.6 (6)	C2—C11—C10—C9	−179.8 (4)
C3—C2—C11—C10	177.6 (4)	C1—N1—C12—C13	−140.1 (4)
C1—C2—C11—C6	175.9 (4)	O1—C3—C4—C5	178.5 (4)
C3—C2—C11—C6	−0.9 (6)	C2—C3—C4—C5	−1.1 (7)
C12—N1—C1—C2	177.0 (4)	C3—C4—C5—C6	−0.8 (7)
C3—C2—C1—N1	−3.4 (6)	C7—C6—C5—C4	−179.3 (5)
C11—C2—C1—N1	179.8 (4)	C11—C6—C5—C4	1.8 (7)
C10—C11—C6—C7	1.5 (6)	C9—C8—C7—C6	0.3 (7)
C2—C11—C6—C7	−179.9 (4)	C11—C6—C7—C8	−1.1 (7)
C10—C11—C6—C5	−179.5 (4)	C5—C6—C7—C8	180.0 (4)
C2—C11—C6—C5	−0.9 (6)	C11—C10—C9—C8	0.5 (7)
C1—C2—C3—O1	5.5 (6)	C7—C8—C9—C10	0.0 (7)
C11—C2—C3—O1	−177.7 (4)	C14—O2—C13—C12	179.6 (3)
C1—C2—C3—C4	−175.0 (4)	N1—C12—C13—O2	−61.2 (5)
C11—C2—C3—C4	1.8 (6)	C13—O2—C14—C14i	−179.5 (4)
C6—C11—C10—C9	−1.3 (6)

Symmetry codes: (i) −x+1/2, −y+1, z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	1.85	2.542 (5)	136
C14—H14B···O2ii	0.97	2.58	3.382 (5)	141
C12—H12B···O1iii	0.97	2.50	3.257 (5)	134

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