2,2′-[Ethyl­enebis(azanediyl­methyl­ene)]diphenol

Xu, Y.-M.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809048831

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3151

doi:10.1107/S1600536809048831

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2,2′-[Ethylenebis(azanediylmethylene)]diphenol

Ying-Ming Xu,^a Shan Gao ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 16 November 2009; accepted 17 November 2009; online 21 November 2009)

In the title compound, C₁₆H₂₀N₂O₄, the molecule features a zigzag –CH₂–NH–CH₂–CH₂–NH–CH₂– chain whose ends are connected to the hydroxyphenyl rings. The molecules lies about a center of inversion. The imino group is a hydrogen-bond donor for the hydroxy group, which is a hydrogen-bond donor for the imino group of an adjacent molecule. This latter intermolecular hydrogen bonding leads to a layer structure.

Related literature

The title compound was doubly-deprotonated, forming several tetradentate chelated metal complexes. For their crystal structures, see: Atwood et al. (1995 , 1996 ); Borer et al. (1983 ); Bottcher et al. (1994 ); García-Zarracino et al. (2002 ); Henrick et al. (1984 ); Viswanathan et al. (1998 ); Xie et al. (2006 ); Yang et al. (2007 ).

Experimental

Crystal data

C₁₆H₂₀N₂O₂
M_r = 272.34
Monoclinic, P 2₁ /c
a = 15.263 (2) Å
b = 4.860 (1) Å
c = 9.770 (1) Å
β = 96.318 (3)°
V = 720.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.31 × 0.27 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.975, T_max = 0.979
6726 measured reflections
1635 independent reflections
912 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.176
S = 1.09
1635 reflections
99 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1ⁱ	0.86 (1)	1.89 (1)	2.721 (2)	165 (3)
N1—H1n⋯O1	0.86 (1)	2.23 (2)	2.884 (2)	133 (2)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048831/xu2679sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048831/xu2679Isup2.hkl

checkCIF report

Related literature top

The title compound was doubly-deprotonated, forming several tetradentate chelated metal complexes. For their crystal structures, see: Atwood et al. (1995, 1996); Borer et al. (1983); Bottcher et al. (1994); García-Zarracino et al. (2002); Henrick et al. (1984); Viswanathan et al. (1998); Xie et al. (2006); Yang et al. (2007).

Experimental top

To a solution of salicylaldehyde (2.44 g, 20 mmol) in methanol was added a solution of ethylenediamine (0.6 ml, 10 mmol) in methanol. The solution was heated for two hours. The yellow Schiff base that was isolated upon evaporation of the solvent was reduced in absolute methanol by sodium borohydride. Colorless prismatic crystals were grown from a solution of the diamine in methanol.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the molecule of C₁₆H₂₀N₂O₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2,2'-[Ethylenebis(azanediylmethylene)]diphenol top

Crystal data top

C₁₆H₂₀N₂O₂	F(000) = 292
M_r = 272.34	D_x = 1.256 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3415 reflections
a = 15.263 (2) Å	θ = 4.0–27.4°
b = 4.860 (1) Å	µ = 0.08 mm⁻¹
c = 9.770 (1) Å	T = 293 K
β = 96.318 (3)°	Prism, colorless
V = 720.3 (2) Å³	0.31 × 0.27 × 0.25 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1635 independent reflections
Radiation source: fine-focus sealed tube	912 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ω scan	θ_max = 27.4°, θ_min = 4.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −19→19
T_min = 0.975, T_max = 0.979	k = −6→6
6726 measured reflections	l = −12→11

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0749P)² + 0.1302P] where P = (F_o² + 2F_c²)/3
1635 reflections	(Δ/σ)_max = 0.001
99 parameters	Δρ_max = 0.21 e Å⁻³
2 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₂₀N₂O₂	V = 720.3 (2) Å³
M_r = 272.34	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.263 (2) Å	µ = 0.08 mm⁻¹
b = 4.860 (1) Å	T = 293 K
c = 9.770 (1) Å	0.31 × 0.27 × 0.25 mm
β = 96.318 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1635 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	912 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.979	R_int = 0.055
6726 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	2 restraints
wR(F²) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.21 e Å⁻³
1635 reflections	Δρ_min = −0.19 e Å⁻³
99 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.34270 (10)	0.3118 (4)	0.13029 (16)	0.0555 (5)
N1	0.38397 (11)	0.4899 (4)	0.41165 (18)	0.0451 (5)
C1	0.25836 (14)	0.3821 (5)	0.1507 (2)	0.0439 (6)
C2	0.18572 (15)	0.2708 (5)	0.0744 (2)	0.0552 (6)
H2A	0.1932	0.1404	0.0070	0.066*
C3	0.10190 (15)	0.3510 (6)	0.0972 (3)	0.0622 (7)
H3	0.0532	0.2732	0.0460	0.075*
C4	0.09036 (16)	0.5466 (6)	0.1958 (3)	0.0624 (7)
H4	0.0340	0.6040	0.2103	0.075*
C5	0.16325 (16)	0.6564 (5)	0.2727 (2)	0.0564 (7)
H5	0.1552	0.7871	0.3397	0.068*
C6	0.24808 (13)	0.5773 (5)	0.2530 (2)	0.0443 (6)
C7	0.32748 (15)	0.6983 (5)	0.3364 (2)	0.0524 (6)
H7A	0.3621	0.7987	0.2754	0.063*
H7B	0.3079	0.8285	0.4019	0.063*
C8	0.46843 (13)	0.6100 (5)	0.4701 (2)	0.0497 (6)
H8A	0.4579	0.7403	0.5418	0.060*
H8B	0.4947	0.7091	0.3988	0.060*
H1O	0.3458 (18)	0.209 (5)	0.0600 (19)	0.081 (10)*
H1N	0.3943 (15)	0.370 (4)	0.3504 (19)	0.060 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0458 (10)	0.0730 (13)	0.0477 (10)	0.0062 (8)	0.0060 (7)	−0.0106 (8)
N1	0.0441 (10)	0.0469 (12)	0.0432 (10)	−0.0043 (8)	0.0005 (8)	−0.0013 (9)
C1	0.0434 (12)	0.0475 (13)	0.0409 (11)	0.0033 (10)	0.0055 (9)	0.0053 (10)
C2	0.0546 (14)	0.0616 (16)	0.0482 (13)	−0.0008 (11)	−0.0005 (11)	−0.0064 (12)
C3	0.0457 (14)	0.0746 (19)	0.0642 (16)	−0.0037 (12)	−0.0036 (12)	0.0023 (14)
C4	0.0465 (13)	0.0746 (19)	0.0660 (16)	0.0126 (13)	0.0065 (12)	0.0082 (14)
C5	0.0565 (14)	0.0592 (16)	0.0536 (14)	0.0127 (12)	0.0074 (11)	0.0000 (11)
C6	0.0489 (13)	0.0424 (13)	0.0418 (11)	0.0012 (9)	0.0050 (10)	0.0039 (9)
C7	0.0570 (14)	0.0458 (14)	0.0532 (13)	0.0055 (11)	0.0014 (11)	0.0000 (11)
C8	0.0480 (13)	0.0493 (15)	0.0510 (13)	−0.0079 (10)	0.0009 (10)	−0.0009 (11)

Geometric parameters (Å, º) top

O1—C1	1.367 (2)	C4—C5	1.380 (4)
O1—H1O	0.86 (1)	C4—H4	0.9300
N1—C8	1.472 (3)	C5—C6	1.384 (3)
N1—C7	1.473 (3)	C5—H5	0.9300
N1—H1N	0.86 (1)	C6—C7	1.504 (3)
C1—C2	1.377 (3)	C7—H7A	0.9700
C1—C6	1.399 (3)	C7—H7B	0.9700
C2—C3	1.379 (3)	C8—C8ⁱ	1.513 (4)
C2—H2A	0.9300	C8—H8A	0.9700
C3—C4	1.379 (4)	C8—H8B	0.9700
C3—H3	0.9300

C1—O1—H1O	113.5 (19)	C4—C5—H5	119.1
C8—N1—C7	111.12 (17)	C6—C5—H5	119.1
C8—N1—H1N	108.6 (16)	C5—C6—C1	117.9 (2)
C7—N1—H1N	105.1 (16)	C5—C6—C7	121.7 (2)
O1—C1—C2	122.6 (2)	C1—C6—C7	120.34 (19)
O1—C1—C6	117.04 (19)	N1—C7—C6	113.21 (18)
C2—C1—C6	120.4 (2)	N1—C7—H7A	108.9
C1—C2—C3	120.5 (2)	C6—C7—H7A	108.9
C1—C2—H2A	119.7	N1—C7—H7B	108.9
C3—C2—H2A	119.7	C6—C7—H7B	108.9
C2—C3—C4	120.0 (2)	H7A—C7—H7B	107.8
C2—C3—H3	120.0	N1—C8—C8ⁱ	111.3 (2)
C4—C3—H3	120.0	N1—C8—H8A	109.4
C3—C4—C5	119.4 (2)	C8ⁱ—C8—H8A	109.4
C3—C4—H4	120.3	N1—C8—H8B	109.4
C5—C4—H4	120.3	C8ⁱ—C8—H8B	109.4
C4—C5—C6	121.8 (2)	H8A—C8—H8B	108.0

O1—C1—C2—C3	−179.0 (2)	C2—C1—C6—C5	−1.0 (3)
C6—C1—C2—C3	0.4 (4)	O1—C1—C6—C7	−0.7 (3)
C1—C2—C3—C4	0.8 (4)	C2—C1—C6—C7	179.9 (2)
C2—C3—C4—C5	−1.2 (4)	C8—N1—C7—C6	169.35 (18)
C3—C4—C5—C6	0.6 (4)	C5—C6—C7—N1	122.4 (2)
C4—C5—C6—C1	0.6 (4)	C1—C6—C7—N1	−58.5 (3)
C4—C5—C6—C7	179.7 (2)	C7—N1—C8—C8ⁱ	−171.9 (2)
O1—C1—C6—C5	178.39 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1ⁱⁱ	0.86 (1)	1.89 (1)	2.721 (2)	165 (3)
N1—H1n···O1	0.86 (1)	2.23 (2)	2.884 (2)	133 (2)

Symmetry code: (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₂₀N₂O₂
M_r	272.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.263 (2), 4.860 (1), 9.770 (1)
β (°)	96.318 (3)
V (Å³)	720.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.31 × 0.27 × 0.25

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.975, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	6726, 1635, 912
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.176, 1.09
No. of reflections	1635
No. of parameters	99
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1ⁱ	0.86 (1)	1.89 (1)	2.721 (2)	165 (3)
N1—H1n···O1	0.86 (1)	2.23 (2)	2.884 (2)	133 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Scientific Fund of Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this study.

References

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