organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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[Atwood, D. A., Jegier, J. A., Martin, K. J. & Rutherford, D. (1995). J. Organomet. Chem. 503, C4-C7.], 1996[Atwood, D. A., Jegier, J. A., Lindholm, N. F., Martin, K. J. & Rutherford, D. R. (1996). J. Coord. Chem. 38, 305-318.]); Borer et al. (1983[Borer, L., Thalken, L., Ceccarelli, C., Glick, M., Zhang, J. H. & Reiff, W. M. (1983). Inorg. Chem. 22, 1719-1724.]); Bottcher et al. (1994[Bottcher, A., Elias, H., Glerup, J., Neuburger, M., Olsen, C. E., Paulus, H., Sprinbborg, J. & Zehinder, M. (1994). Acta Chem. Scand. 48, 967-980.]); García-Zarracino et al. (2002[García-Zarracino, R., Ramos-Quiñones, J. & Höpfl, H. (2002). J. Organomet. Chem. 664, 188-200.]); Henrick et al. (1984[Henrick, K., Lindoy, L. F., McPartlin, M., Tasker, P. A. & Wood, M. P. (1984). J. Am. Chem. Soc. 106, 1641-1645.]); Viswanathan et al. (1998[Viswanathan, R., Palaniandavar, M., Prabakaran, P. & Muthiah, P. T. (1998). Inorg. Chem. 37, 3881-3884.]); Xie et al. (2006[Xie, Y.-S., Liu, Q.-L., Jiang, H., Ni, J., Hui, J. & Jia, N. (2006). Eur. J. Inorg. Chem. pp. 4010-4016.]); Yang et al. (2007[Yang, S.-P., Han, L.-J., Wang, D.-Q. & Wang, B. (2007). Acta Cryst. E63, m2777-m2778.]).

[Scheme 1]

Experimental

Crystal data
  • C16H20N2O2

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.975, Tmax = 0.979

  • 6726 measured reflections

  • 1635 independent reflections

  • 912 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


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.

Refinement top

Carbon-bound H-atoms generated geometrically (0.93–0.97 Å, Uiso(H) = 1.2Ueq(C)). The nitrogen- and oxygen-bound H-atoms were refined with a distance restraint of N–H = O–H = 0.85±0.01 Å; their temperature factors were refined.

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
[Figure 1] 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
C16H20N2O2F(000) = 292
Mr = 272.34Dx = 1.256 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3415 reflections
a = 15.263 (2) Åθ = 4.0–27.4°
b = 4.860 (1) ŵ = 0.08 mm1
c = 9.770 (1) ÅT = 293 K
β = 96.318 (3)°Prism, colorless
V = 720.3 (2) Å30.31 × 0.27 × 0.25 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer
1635 independent reflections
Radiation source: fine-focus sealed tube912 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ω scanθmax = 27.4°, θmin = 4.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1919
Tmin = 0.975, Tmax = 0.979k = 66
6726 measured reflectionsl = 1211
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0749P)2 + 0.1302P]
where P = (Fo2 + 2Fc2)/3
1635 reflections(Δ/σ)max = 0.001
99 parametersΔρmax = 0.21 e Å3
2 restraintsΔρmin = 0.19 e Å3
Crystal data top
C16H20N2O2V = 720.3 (2) Å3
Mr = 272.34Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.263 (2) ŵ = 0.08 mm1
b = 4.860 (1) ÅT = 293 K
c = 9.770 (1) Å0.31 × 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)
Tmin = 0.975, Tmax = 0.979Rint = 0.055
6726 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0522 restraints
wR(F2) = 0.176H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.21 e Å3
1635 reflectionsΔρmin = 0.19 e Å3
99 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.34270 (10)0.3118 (4)0.13029 (16)0.0555 (5)
N10.38397 (11)0.4899 (4)0.41165 (18)0.0451 (5)
C10.25836 (14)0.3821 (5)0.1507 (2)0.0439 (6)
C20.18572 (15)0.2708 (5)0.0744 (2)0.0552 (6)
H2A0.19320.14040.00700.066*
C30.10190 (15)0.3510 (6)0.0972 (3)0.0622 (7)
H30.05320.27320.04600.075*
C40.09036 (16)0.5466 (6)0.1958 (3)0.0624 (7)
H40.03400.60400.21030.075*
C50.16325 (16)0.6564 (5)0.2727 (2)0.0564 (7)
H50.15520.78710.33970.068*
C60.24808 (13)0.5773 (5)0.2530 (2)0.0443 (6)
C70.32748 (15)0.6983 (5)0.3364 (2)0.0524 (6)
H7A0.36210.79870.27540.063*
H7B0.30790.82850.40190.063*
C80.46843 (13)0.6100 (5)0.4701 (2)0.0497 (6)
H8A0.45790.74030.54180.060*
H8B0.49470.70910.39880.060*
H1O0.3458 (18)0.209 (5)0.0600 (19)0.081 (10)*
H1N0.3943 (15)0.370 (4)0.3504 (19)0.060 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0458 (10)0.0730 (13)0.0477 (10)0.0062 (8)0.0060 (7)0.0106 (8)
N10.0441 (10)0.0469 (12)0.0432 (10)0.0043 (8)0.0005 (8)0.0013 (9)
C10.0434 (12)0.0475 (13)0.0409 (11)0.0033 (10)0.0055 (9)0.0053 (10)
C20.0546 (14)0.0616 (16)0.0482 (13)0.0008 (11)0.0005 (11)0.0064 (12)
C30.0457 (14)0.0746 (19)0.0642 (16)0.0037 (12)0.0036 (12)0.0023 (14)
C40.0465 (13)0.0746 (19)0.0660 (16)0.0126 (13)0.0065 (12)0.0082 (14)
C50.0565 (14)0.0592 (16)0.0536 (14)0.0127 (12)0.0074 (11)0.0000 (11)
C60.0489 (13)0.0424 (13)0.0418 (11)0.0012 (9)0.0050 (10)0.0039 (9)
C70.0570 (14)0.0458 (14)0.0532 (13)0.0055 (11)0.0014 (11)0.0000 (11)
C80.0480 (13)0.0493 (15)0.0510 (13)0.0079 (10)0.0009 (10)0.0009 (11)
Geometric parameters (Å, º) top
O1—C11.367 (2)C4—C51.380 (4)
O1—H1O0.86 (1)C4—H40.9300
N1—C81.472 (3)C5—C61.384 (3)
N1—C71.473 (3)C5—H50.9300
N1—H1N0.86 (1)C6—C71.504 (3)
C1—C21.377 (3)C7—H7A0.9700
C1—C61.399 (3)C7—H7B0.9700
C2—C31.379 (3)C8—C8i1.513 (4)
C2—H2A0.9300C8—H8A0.9700
C3—C41.379 (4)C8—H8B0.9700
C3—H30.9300
C1—O1—H1O113.5 (19)C4—C5—H5119.1
C8—N1—C7111.12 (17)C6—C5—H5119.1
C8—N1—H1N108.6 (16)C5—C6—C1117.9 (2)
C7—N1—H1N105.1 (16)C5—C6—C7121.7 (2)
O1—C1—C2122.6 (2)C1—C6—C7120.34 (19)
O1—C1—C6117.04 (19)N1—C7—C6113.21 (18)
C2—C1—C6120.4 (2)N1—C7—H7A108.9
C1—C2—C3120.5 (2)C6—C7—H7A108.9
C1—C2—H2A119.7N1—C7—H7B108.9
C3—C2—H2A119.7C6—C7—H7B108.9
C2—C3—C4120.0 (2)H7A—C7—H7B107.8
C2—C3—H3120.0N1—C8—C8i111.3 (2)
C4—C3—H3120.0N1—C8—H8A109.4
C3—C4—C5119.4 (2)C8i—C8—H8A109.4
C3—C4—H4120.3N1—C8—H8B109.4
C5—C4—H4120.3C8i—C8—H8B109.4
C4—C5—C6121.8 (2)H8A—C8—H8B108.0
O1—C1—C2—C3179.0 (2)C2—C1—C6—C51.0 (3)
C6—C1—C2—C30.4 (4)O1—C1—C6—C70.7 (3)
C1—C2—C3—C40.8 (4)C2—C1—C6—C7179.9 (2)
C2—C3—C4—C51.2 (4)C8—N1—C7—C6169.35 (18)
C3—C4—C5—C60.6 (4)C5—C6—C7—N1122.4 (2)
C4—C5—C6—C10.6 (4)C1—C6—C7—N158.5 (3)
C4—C5—C6—C7179.7 (2)C7—N1—C8—C8i171.9 (2)
O1—C1—C6—C5178.39 (19)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···N1ii0.86 (1)1.89 (1)2.721 (2)165 (3)
N1—H1n···O10.86 (1)2.23 (2)2.884 (2)133 (2)
Symmetry code: (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC16H20N2O2
Mr272.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)15.263 (2), 4.860 (1), 9.770 (1)
β (°) 96.318 (3)
V3)720.3 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.31 × 0.27 × 0.25
Data collection
DiffractometerRigaku R-AXIS RAPID IP
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.975, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
6726, 1635, 912
Rint0.055
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.176, 1.09
No. of reflections1635
No. of parameters99
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O1—H1o···N1i0.86 (1)1.89 (1)2.721 (2)165 (3)
N1—H1n···O10.86 (1)2.23 (2)2.884 (2)133 (2)
Symmetry code: (i) x, y+1/2, z1/2.
 

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

First citationAtwood, D. A., Jegier, J. A., Lindholm, N. F., Martin, K. J. & Rutherford, D. R. (1996). J. Coord. Chem. 38, 305–318.  CrossRef CAS Web of Science Google Scholar
First citationAtwood, D. A., Jegier, J. A., Martin, K. J. & Rutherford, D. (1995). J. Organomet. Chem. 503, C4–C7.  CrossRef CAS Web of Science Google Scholar
First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBorer, L., Thalken, L., Ceccarelli, C., Glick, M., Zhang, J. H. & Reiff, W. M. (1983). Inorg. Chem. 22, 1719–1724.  CSD CrossRef CAS Web of Science Google Scholar
First citationBottcher, A., Elias, H., Glerup, J., Neuburger, M., Olsen, C. E., Paulus, H., Sprinbborg, J. & Zehinder, M. (1994). Acta Chem. Scand. 48, 967–980.  CrossRef Web of Science Google Scholar
First citationGarcía-Zarracino, R., Ramos-Quiñones, J. & Höpfl, H. (2002). J. Organomet. Chem. 664, 188–200.  Web of Science CSD CrossRef Google Scholar
First citationHenrick, K., Lindoy, L. F., McPartlin, M., Tasker, P. A. & Wood, M. P. (1984). J. Am. Chem. Soc. 106, 1641–1645.  CSD CrossRef CAS Web of Science Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationViswanathan, R., Palaniandavar, M., Prabakaran, P. & Muthiah, P. T. (1998). Inorg. Chem. 37, 3881–3884.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar
First citationXie, Y.-S., Liu, Q.-L., Jiang, H., Ni, J., Hui, J. & Jia, N. (2006). Eur. J. Inorg. Chem. pp. 4010–4016.  Google Scholar
First citationYang, S.-P., Han, L.-J., Wang, D.-Q. & Wang, B. (2007). Acta Cryst. E63, m2777–m2778.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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