1,1′-{(1E,1′E)-[Octane-1,8-diylbis(aza­nylyl­idene)]bis­(methanylyl­idene)}bis­(naphthalen-2-ol) in the zwitterionic form

Bendia, S.; Ouari, K.; Karmazin, L.

doi:10.1107/S2414314617001699

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170169

https://doi.org/10.1107/S2414314617001699

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1,1′-{(1E,1′E)-[Octane-1,8-diylbis(azanylylidene)]bis(methanylylidene)}bis(naphthalen-2-ol) in the zwitterionic form

Sabrina Bendia,^a Kamel Ouari ^a ^* and Lydia Karmazin ^b

^aLaboratoire d'Electrochimie, d'Ingénierie Moléculaire et de Catalyse Redox, Faculty of Technology, University of Ferhat Abbas Sétif-1, 19000-Sétif, Algeria, and ^bInstitut de Chimie de Strasbourg, UMR 7177 CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France
^*Correspondence e-mail: k_ouari@yahoo.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 20 January 2017; accepted 31 January 2017; online 3 February 2017)

The title compound, C₃₀H₃₂O₂N₂, is formed from two units of ortho-hydroxynaphthaldehyde bridged with 1,8-diaminooctane. In the solid state, it exists as a double zwitterion. The N atoms are protonated and the C—O⁻ bonds lengths are 1.265 (2) Å, with intramolecular N—H⋯O hydrogen bonds forming S(6) ring motifs. The molecule has twofold rotational symmetry, with the twofold axis bisecting the central –CH₂—CH₂– bond of the bridging octane chain. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating along the [-201] direction. The chains are linked via C—H⋯O hydrogen bonds, forming a supramolecular three-dimensional framework structure.

Keywords: crystal structure; zwitterion; 1,8-diaminooctane; 2-hydroxy-1-naphthaldehyde; hydrogen bonding; elemental analysis; NMR spectroscopy.

CCDC reference: 1530499

Structure description

Recently, our group has reported the crystal structures of four new Schiff bases, synthesized using literature methods by reacting primary amines and o-hydroxynaphthaldehyde (Merzougui et al., 2016 ; Ouari et al., 2015a ,b ,c ). They crystallize as bis-zwitterionic compounds with strong intramolecular N—H⋯O hydrogen bonds, forming S(6) ring motifs. Such compounds are of interest because the azomethine C=N and C—O groups form stable transition metal complexes by coordinating through the nitrogen and oxygen atoms (Ouari et al., 2010 , 2015d ).

The title compound is formed from two units of ortho-hydroxynaphthaldehyde bridged with 1,8-diaminooctane. The molecule has twofold rotational symmetry with the twofold axis bisecting the central –C15—C15ⁱ– bond [symmetry code (i): −x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1]. Atoms N1 and N1ⁱ are protonated and the C1—O1 and C1ⁱ—O1ⁱ bond lengths are 1.265 (2) Å, hence the compound has crystallized as a double zwitterion with intramolecular N—H⋯O hydrogen bonds forming S(6) ring motifs (Table 1 and Fig. 1). This is similar to the structures of the compounds mentioned above.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.93 (2)	1.87 (2)	2.602 (2)	133.6 (18)
N1—H1N⋯O1ⁱⁱ	0.93 (2)	2.44 (2)	3.115 (2)	129.6 (17)
C12—H12A⋯O1ⁱⁱⁱ	0.99	2.47	3.201 (2)	131
Symmetry codes: (ii) -x, -y+2, -z; (iii) $[x, -y+2, z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by twofold rotation symmetry (−x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1). The intramolecular N—H⋯O hydrogen bonds are shown as dashed lines (see Table 1

In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating along [ $[\overline{2}]$ 01] and enclosing R₂²(4) ring motifs (Table 1 and Fig. 2). The chains are linked via C—H⋯O hydrogen bonds, forming a supramolecular three-dimensional framework structure (Table 1 and Fig. 3).

Figure 2
A partial view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1

), and for clarity, only H atoms H1N and H12A (grey balls) have been included.

Figure 3
Crystal packing of the title compound, viewed along the c axis. The hydrogen bonds are shown as dashed lines (see Table 1

), and for clarity, only H atoms H1N and H12A (grey balls) have been included.

Synthesis and crystallization

The title Schiff base was prepared by condensation between 1,8-diaminooctane (72 mg, 0.5 mmol) and 2-hydroxy-1-naphthaldehyde (172 mg, 1 mmol) in methanol (10 ml). The mixture was refluxed and stirred under a nitrogen atmosphere for 2 h. The precipitate obtained was filtered, washed with methanol and diethyl ether and dried in vacuum overnight. Yellow single crystals of the title compound were obtained by slow evaporation of a solution in methanol (yield 71%; m.p. 438–440 K). Elemental analysis: calculated for C₃₀H₃₂O₂N₂: C 79.63, H 7.23, N 6.16%; found: C 79.61, H 7.13, N 6.19%.

¹H NMR: (DMSO-d₆, δ p.p.m.): 14.12 (C—OH), 9.07 (s, CH=N), 6.40–8.40 (m, ArH), 1.00–4.00 (m, aliphH); ¹³C NMR: (DMSO-d₆, δ p.p.m.): 178.04 (C—O), 159.35 (CH=N), 100–140 (C—Ar), 23.57–55.12 (C-aliphat). The DEPT-135 spectrum shows a disappearance of resonances at 106.07, 125.46, 134.81 and 178.28 p.p.m.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₃₀H₃₂N₂O₂
M_r	452.58
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	18.0993 (12), 14.2646 (9), 9.5990 (6)
β (°)	105.345 (1)
V (Å³)	2389.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2010 )
T_min, T_max	0.973, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	20784, 2907, 2159
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.663

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.146, 1.13
No. of reflections	2907
No. of parameters	158
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2010), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1530499

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314617001699/su4126sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001699/su4126Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617001699/su4126Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1,1'-{(1E,1'E)-[Octane-1,8-diylbis(azanylylidene)]bis(methanylylidene)}bis(naphthalen-2-ol) in the zwitterion form top

Crystal data top

C₃₀H₃₂N₂O₂	F(000) = 968
M_r = 452.58	D_x = 1.258 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6936 reflections
a = 18.0993 (12) Å	θ = 2.3–28.0°
b = 14.2646 (9) Å	µ = 0.08 mm⁻¹
c = 9.5990 (6) Å	T = 173 K
β = 105.345 (1)°	Prism, yellow
V = 2389.9 (3) Å³	0.35 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2907 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 28.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −22→23
T_min = 0.973, T_max = 0.985	k = −18→14
20784 measured reflections	l = −12→10

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0442P)² + 2.0625P] where P = (F_o² + 2F_c²)/3
2907 reflections	(Δ/σ)_max < 0.001
158 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C1	0.03219 (9)	1.19048 (15)	0.05578 (16)	0.0474 (5)
C2	0.01367 (10)	1.27725 (17)	−0.02317 (18)	0.0576 (6)
H2	−0.0178	1.2756	−0.1196	0.069*
C3	0.03949 (10)	1.35977 (17)	0.0356 (2)	0.0595 (6)
H3	0.0264	1.4148	−0.0214	0.071*
C4	0.08643 (9)	1.36885 (14)	0.18190 (19)	0.0488 (4)
C5	0.10920 (11)	1.45675 (16)	0.2428 (2)	0.0610 (5)
H5	0.0944	1.5117	0.1863	0.073*
C6	0.15275 (11)	1.46479 (16)	0.3835 (3)	0.0628 (6)
H6	0.1677	1.5248	0.4242	0.075*
C7	0.17461 (10)	1.38405 (14)	0.4656 (2)	0.0524 (5)
H7	0.2045	1.3893	0.5628	0.063*
C8	0.15364 (9)	1.29760 (13)	0.40838 (17)	0.0441 (4)
H8	0.1696	1.2436	0.4665	0.053*
C9	0.10847 (8)	1.28615 (13)	0.26391 (16)	0.0401 (4)
C10	0.08336 (8)	1.19633 (13)	0.19953 (15)	0.0397 (4)
C11	0.10777 (8)	1.11267 (13)	0.27413 (16)	0.0413 (4)
H11	0.1414	1.1180	0.3684	0.050*
C12	0.11699 (10)	0.94316 (14)	0.30608 (17)	0.0478 (4)
H12A	0.0730	0.9030	0.3101	0.057*
H12B	0.1446	0.9600	0.4064	0.057*
C13	0.17022 (10)	0.88827 (14)	0.23865 (17)	0.0481 (4)
H13A	0.2175	0.9251	0.2467	0.058*
H13B	0.1452	0.8790	0.1347	0.058*
C14	0.19159 (10)	0.79304 (14)	0.30986 (17)	0.0493 (5)
H14A	0.2201	0.7571	0.2526	0.059*
H14B	0.1439	0.7581	0.3070	0.059*
C15	0.24003 (9)	0.79781 (13)	0.46606 (16)	0.0461 (4)
H15A	0.2880	0.8321	0.4694	0.055*
H15B	0.2118	0.8337	0.5237	0.055*
N1	0.08863 (8)	1.02829 (11)	0.22613 (15)	0.0460 (4)
O1	0.00462 (7)	1.11356 (11)	−0.00035 (12)	0.0605 (4)
H1N	0.0548 (13)	1.0243 (15)	0.135 (2)	0.067 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0272 (7)	0.0888 (14)	0.0267 (7)	0.0027 (8)	0.0080 (6)	−0.0046 (8)
C2	0.0343 (9)	0.1043 (17)	0.0311 (8)	0.0120 (10)	0.0034 (6)	0.0074 (10)
C3	0.0359 (9)	0.0938 (16)	0.0482 (10)	0.0212 (10)	0.0101 (8)	0.0201 (11)
C4	0.0300 (8)	0.0695 (13)	0.0489 (9)	0.0141 (8)	0.0141 (7)	0.0069 (9)
C5	0.0461 (10)	0.0653 (13)	0.0736 (13)	0.0165 (9)	0.0192 (10)	0.0100 (11)
C6	0.0490 (11)	0.0615 (13)	0.0805 (15)	0.0027 (9)	0.0217 (10)	−0.0120 (11)
C7	0.0392 (9)	0.0656 (12)	0.0516 (10)	−0.0006 (8)	0.0108 (8)	−0.0106 (9)
C8	0.0345 (8)	0.0605 (11)	0.0371 (8)	0.0010 (7)	0.0090 (6)	−0.0031 (7)
C9	0.0237 (7)	0.0641 (11)	0.0347 (7)	0.0066 (7)	0.0112 (6)	−0.0004 (7)
C10	0.0242 (7)	0.0693 (11)	0.0264 (7)	0.0028 (7)	0.0081 (5)	−0.0024 (7)
C11	0.0288 (7)	0.0689 (11)	0.0266 (7)	−0.0028 (7)	0.0080 (6)	−0.0065 (7)
C12	0.0483 (10)	0.0646 (12)	0.0320 (8)	−0.0091 (8)	0.0132 (7)	−0.0030 (7)
C13	0.0437 (9)	0.0713 (12)	0.0291 (7)	−0.0052 (8)	0.0092 (7)	0.0001 (8)
C14	0.0439 (9)	0.0703 (13)	0.0301 (8)	−0.0067 (8)	0.0035 (7)	−0.0045 (8)
C15	0.0367 (8)	0.0679 (12)	0.0308 (8)	−0.0134 (8)	0.0036 (6)	−0.0035 (7)
N1	0.0397 (7)	0.0694 (10)	0.0281 (6)	−0.0057 (7)	0.0076 (5)	−0.0049 (7)
O1	0.0425 (7)	0.1048 (12)	0.0307 (6)	−0.0068 (7)	0.0037 (5)	−0.0135 (7)

Geometric parameters (Å, º) top

C1—O1	1.265 (2)	C10—C11	1.402 (2)
C1—C2	1.444 (3)	C11—N1	1.303 (2)
C1—C10	1.446 (2)	C11—H11	0.9500
C2—C3	1.335 (3)	C12—N1	1.455 (2)
C2—H2	0.9500	C12—C13	1.513 (2)
C3—C4	1.442 (3)	C12—H12A	0.9900
C3—H3	0.9500	C12—H12B	0.9900
C4—C5	1.399 (3)	C13—C14	1.524 (3)
C4—C9	1.416 (2)	C13—H13A	0.9900
C5—C6	1.377 (3)	C13—H13B	0.9900
C5—H5	0.9500	C14—C15	1.525 (2)
C6—C7	1.392 (3)	C14—H14A	0.9900
C6—H6	0.9500	C14—H14B	0.9900
C7—C8	1.363 (3)	C15—C15ⁱ	1.514 (4)
C7—H7	0.9500	C15—H15A	0.9900
C8—C9	1.421 (2)	C15—H15B	0.9900
C8—H8	0.9500	N1—H1N	0.93 (2)
C9—C10	1.443 (2)

O1—C1—C2	120.62 (15)	N1—C11—C10	126.00 (14)
O1—C1—C10	122.48 (18)	N1—C11—H11	117.0
C2—C1—C10	116.90 (18)	C10—C11—H11	117.0
C3—C2—C1	121.84 (16)	N1—C12—C13	112.44 (13)
C3—C2—H2	119.1	N1—C12—H12A	109.1
C1—C2—H2	119.1	C13—C12—H12A	109.1
C2—C3—C4	122.73 (19)	N1—C12—H12B	109.1
C2—C3—H3	118.6	C13—C12—H12B	109.1
C4—C3—H3	118.6	H12A—C12—H12B	107.8
C5—C4—C9	120.40 (17)	C12—C13—C14	112.59 (14)
C5—C4—C3	121.34 (19)	C12—C13—H13A	109.1
C9—C4—C3	118.25 (19)	C14—C13—H13A	109.1
C6—C5—C4	120.9 (2)	C12—C13—H13B	109.1
C6—C5—H5	119.5	C14—C13—H13B	109.1
C4—C5—H5	119.5	H13A—C13—H13B	107.8
C5—C6—C7	119.3 (2)	C13—C14—C15	114.38 (15)
C5—C6—H6	120.3	C13—C14—H14A	108.7
C7—C6—H6	120.3	C15—C14—H14A	108.7
C8—C7—C6	120.89 (18)	C13—C14—H14B	108.7
C8—C7—H7	119.6	C15—C14—H14B	108.7
C6—C7—H7	119.6	H14A—C14—H14B	107.6
C7—C8—C9	121.64 (17)	C15ⁱ—C15—C14	113.11 (18)
C7—C8—H8	119.2	C15ⁱ—C15—H15A	109.0
C9—C8—H8	119.2	C14—C15—H15A	109.0
C4—C9—C8	116.85 (17)	C15ⁱ—C15—H15B	109.0
C4—C9—C10	119.43 (15)	C14—C15—H15B	109.0
C8—C9—C10	123.70 (16)	H15A—C15—H15B	107.8
C11—C10—C9	121.09 (13)	C11—N1—C12	124.11 (14)
C11—C10—C1	118.29 (16)	C11—N1—H1N	116.0 (13)
C9—C10—C1	120.63 (16)	C12—N1—H1N	119.9 (13)

O1—C1—C2—C3	177.27 (16)	C4—C9—C10—C11	176.09 (13)
C10—C1—C2—C3	−3.0 (2)	C8—C9—C10—C11	−5.2 (2)
C1—C2—C3—C4	−1.0 (3)	C4—C9—C10—C1	−3.9 (2)
C2—C3—C4—C5	−176.55 (17)	C8—C9—C10—C1	174.82 (13)
C2—C3—C4—C9	2.7 (3)	O1—C1—C10—C11	5.2 (2)
C9—C4—C5—C6	−0.6 (3)	C2—C1—C10—C11	−174.52 (14)
C3—C4—C5—C6	178.70 (17)	O1—C1—C10—C9	−174.87 (14)
C4—C5—C6—C7	0.3 (3)	C2—C1—C10—C9	5.5 (2)
C5—C6—C7—C8	0.2 (3)	C9—C10—C11—N1	−179.99 (14)
C6—C7—C8—C9	−0.4 (3)	C1—C10—C11—N1	0.0 (2)
C5—C4—C9—C8	0.3 (2)	N1—C12—C13—C14	−172.37 (14)
C3—C4—C9—C8	−179.00 (14)	C12—C13—C14—C15	−66.4 (2)
C5—C4—C9—C10	179.08 (15)	C13—C14—C15—C15ⁱ	179.72 (17)
C3—C4—C9—C10	−0.2 (2)	C10—C11—N1—C12	178.34 (14)
C7—C8—C9—C4	0.2 (2)	C13—C12—N1—C11	−111.09 (17)
C7—C8—C9—C10	−178.53 (15)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.93 (2)	1.87 (2)	2.602 (2)	133.6 (18)
N1—H1N···O1ⁱⁱ	0.93 (2)	2.44 (2)	3.115 (2)	129.6 (17)
C12—H12A···O1ⁱⁱⁱ	0.99	2.47	3.201 (2)	131

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

Acknowledgements

The authors gratefully acknowledge the help of Dr Jean Weiss from the CLAC laboratory at the Institut de Chimie, Université de Strasbourg, France.

Funding information

Funding for this research was provided by: Ministère de l'Enseignement Supérieur et de la Recherche Scientifique

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