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ISSN: 2056-9890

4,4′-Dimeth­­oxy-2,2′-[methyl­aza­ne­diyl­bis­(methyl­ene)]diphenol

aDepartment of Materials and Metallurgical Engineering, Faculty of Engineering, Rajamangala University of Technology Thanyaburi, Pathumthani 12110, Thailand, bDepartment of Materials Engineering, Faculty of Engineering, Kasetsart University, Bangkok 10900, Thailand, and cDepartment of Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand
*Correspondence e-mail: fengapl@ku.ac.th

(Received 11 May 2012; accepted 13 June 2012; online 20 June 2012)

The title compound, C17H21NO4, shows an intra­molecular hydrogen bond between a phenol OH group and the N atom. In the crystal, mol­ecules are connected by pairs of O—H⋯O hydrogen bonds into inversion dimers.

Related literature

For the synthesis of N,N-bis­(2-hy­droxy­benz­yl)alkyl­amines, see: Laobuthee et al. (2003[Laobuthee, A., Ishida, H. & Chirachanchai, S. (2003). J. Incl. Phenom. Macrocycl. Chem. 47, 179-185.]). For their metal-responsive properties, see: Veranitisagul et al. (2011[Veranitisagul, C., Kaewvilai, A., Sangngern, S., Wattanathana, W., Suramitr, S., Koonsaeng, N. & Laobuthee, A. (2011). Int. J. Mol. Sci. 12, 4365-4377.]). For their use in the synthesis of macrocyclic mol­ecules, see: Rungsimanon et al. (2008[Rungsimanon, T., Laobuthee, A., Miyata, M. & Chirachanchai, S. (2008). J. Incl. Phenom. Macrocycl. Chem. 62, 333-338.]).

[Scheme 1]

Experimental

Crystal data
  • C17H21NO4

  • Mr = 303.35

  • Monoclinic, P 21 /c

  • a = 13.3384 (9) Å

  • b = 8.5634 (5) Å

  • c = 14.1021 (8) Å

  • β = 99.340 (2)°

  • V = 1589.42 (17) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 296 K

  • 0.54 × 0.54 × 0.28 mm

Data collection
  • Siemens P4 diffractometer

  • 8022 measured reflections

  • 3649 independent reflections

  • 2711 reflections with I > 2σ(I)

  • Rint = 0.020

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.160

  • S = 1.03

  • 3649 reflections

  • 207 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H′′⋯N 0.98 (3) 1.78 (3) 2.6679 (16) 149 (2)
O1—H′⋯O2i 0.88 (3) 1.89 (3) 2.7550 (16) 169 (2)
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: XSCANS (Siemens, 1992[Siemens (1992). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: XSCANS; data reduction: XSCANS; 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Related literature top

For the synthesis of N,N-bis(2-hydroxybenzyl)alkylamines, see: Laobuthee et al. (2003). For their metal-responsive properties, see: Veranitisagul et al. (2011). For their use in the synthesis of macrocyclic molecules, see: Rungsimanon et al. (2008).

Experimental top

The title compound, N,N-bis(5-methoxy-2-hydroxybenzyl) methylamine was prepared elsewhere (Laobuthee et al., 2003). Recrystallized in 2-propanol, colorless single crystals suitable for X-ray diffraction were obtained by slow evaporation of the solvent after several days.

Refinement top

All H atoms of the compound were placed in the calculated positions with C—H = 0.96 Å and included in the final cycles of refinement in a rigiding model, Uiso(H) = 1.2 Ueq(H). Except H atom of O atoms were located in different Fourier map and restrained to their hosts.

Structure description top

For the synthesis of N,N-bis(2-hydroxybenzyl)alkylamines, see: Laobuthee et al. (2003). For their metal-responsive properties, see: Veranitisagul et al. (2011). For their use in the synthesis of macrocyclic molecules, see: Rungsimanon et al. (2008).

Computing details top

Data collection: XSCANS (Siemens, 1992); cell refinement: XSCANS (Siemens, 1992); data reduction: XSCANS (Siemens, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with labelling and displacement ellipsoids drawn at the 50% probability level.
4,4'-Dimethoxy-2,2'-[methylazanediylbis(methylene)]diphenol top
Crystal data top
C17H21NO4F(000) = 648
Mr = 303.35Dx = 1.268 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.3384 (9) ÅCell parameters from 3446 reflections
b = 8.5634 (5) Åθ = 2.8–27.3°
c = 14.1021 (8) ŵ = 0.09 mm1
β = 99.340 (2)°T = 296 K
V = 1589.42 (17) Å3Block, colourless
Z = 40.54 × 0.54 × 0.28 mm
Data collection top
Siemens P4
diffractometer
2711 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Graphite monochromatorθmax = 27.5°, θmin = 1.6°
ω scansh = 1716
8022 measured reflectionsk = 118
3649 independent reflectionsl = 1812
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0949P)2 + 0.2159P]
where P = (Fo2 + 2Fc2)/3
3649 reflections(Δ/σ)max < 0.001
207 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C17H21NO4V = 1589.42 (17) Å3
Mr = 303.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.3384 (9) ŵ = 0.09 mm1
b = 8.5634 (5) ÅT = 296 K
c = 14.1021 (8) Å0.54 × 0.54 × 0.28 mm
β = 99.340 (2)°
Data collection top
Siemens P4
diffractometer
2711 reflections with I > 2σ(I)
8022 measured reflectionsRint = 0.020
3649 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.160H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.30 e Å3
3649 reflectionsΔρmin = 0.21 e Å3
207 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
xyzUiso*/Ueq
O10.45389 (9)0.03013 (15)0.59042 (8)0.0530 (3)
O20.34001 (8)0.00867 (16)0.40230 (8)0.0589 (4)
C60.33681 (11)0.08049 (17)0.69636 (10)0.0404 (3)
N0.22980 (9)0.08969 (14)0.53635 (8)0.0377 (3)
C10.42488 (11)0.00508 (18)0.67825 (10)0.0418 (3)
C70.27517 (11)0.18108 (17)0.62086 (10)0.0429 (3)
H7A0.22160.23210.64830.051*
H7B0.31850.26160.60090.051*
C80.18208 (11)0.19071 (18)0.45720 (10)0.0435 (3)
H8A0.22380.28260.45370.052*
H8B0.11610.22480.46960.052*
C90.16962 (11)0.10444 (17)0.36246 (10)0.0404 (3)
C50.30850 (12)0.0610 (2)0.78563 (10)0.0469 (4)
H5A0.25070.11150.79900.056*
C40.36425 (13)0.0320 (2)0.85596 (11)0.0494 (4)
O30.33023 (11)0.03631 (18)0.94292 (9)0.0712 (4)
C100.08049 (12)0.1124 (2)0.29590 (11)0.0492 (4)
H10A0.02550.16940.31020.059*
C20.47847 (12)0.0911 (2)0.74694 (12)0.0504 (4)
H2A0.53540.14380.73330.061*
C140.25065 (12)0.01707 (19)0.33939 (10)0.0443 (4)
C30.44897 (12)0.1103 (2)0.83577 (12)0.0515 (4)
H3A0.48580.17540.88150.062*
C130.24199 (14)0.0611 (2)0.25243 (12)0.0543 (4)
H13A0.29590.12070.23820.065*
C120.15387 (15)0.0506 (2)0.18727 (12)0.0579 (4)
H12A0.14870.10200.12860.069*
O40.01176 (13)0.0372 (2)0.13858 (11)0.0920 (5)
C110.07316 (13)0.0356 (2)0.20820 (12)0.0557 (4)
C170.15734 (14)0.0249 (2)0.56118 (13)0.0583 (5)
H17A0.12910.08260.50480.088*
H17B0.10380.02790.58630.088*
H17C0.19140.09530.60880.088*
C150.37548 (17)0.1441 (3)1.01268 (12)0.0693 (5)
H15A0.34480.13461.06940.104*
H15B0.44690.12281.02840.104*
H15C0.36560.24820.98770.104*
C160.08619 (18)0.1436 (3)0.14472 (19)0.0986 (8)
H16A0.14010.13050.09130.148*
H16B0.05880.24710.14350.148*
H16C0.11220.12830.20360.148*
H'0.5192 (19)0.008 (3)0.5987 (15)0.073 (6)*
H''0.323 (2)0.032 (3)0.4657 (19)0.100 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0356 (6)0.0755 (8)0.0493 (6)0.0063 (5)0.0109 (5)0.0030 (5)
O20.0376 (6)0.0946 (10)0.0453 (6)0.0165 (6)0.0090 (5)0.0014 (6)
C60.0375 (7)0.0397 (7)0.0427 (7)0.0025 (6)0.0029 (6)0.0076 (6)
N0.0360 (6)0.0384 (6)0.0387 (6)0.0005 (5)0.0058 (5)0.0017 (5)
C10.0344 (7)0.0474 (8)0.0435 (7)0.0011 (6)0.0055 (6)0.0052 (6)
C70.0419 (8)0.0393 (8)0.0467 (7)0.0051 (6)0.0050 (6)0.0050 (6)
C80.0412 (7)0.0439 (8)0.0450 (7)0.0074 (6)0.0059 (6)0.0043 (6)
C90.0383 (7)0.0410 (8)0.0420 (7)0.0002 (6)0.0069 (6)0.0076 (6)
C50.0448 (8)0.0510 (9)0.0449 (8)0.0096 (7)0.0074 (6)0.0088 (6)
C40.0500 (9)0.0577 (10)0.0404 (7)0.0045 (7)0.0070 (6)0.0038 (7)
O30.0790 (9)0.0930 (10)0.0435 (6)0.0266 (8)0.0159 (6)0.0074 (6)
C100.0409 (8)0.0513 (9)0.0538 (8)0.0043 (7)0.0033 (6)0.0027 (7)
C20.0381 (8)0.0556 (9)0.0578 (9)0.0102 (7)0.0083 (7)0.0000 (7)
C140.0393 (8)0.0524 (9)0.0422 (7)0.0031 (6)0.0095 (6)0.0089 (6)
C30.0467 (9)0.0544 (9)0.0511 (8)0.0087 (7)0.0009 (7)0.0045 (7)
C130.0572 (10)0.0590 (10)0.0490 (8)0.0108 (8)0.0147 (7)0.0017 (7)
C120.0697 (12)0.0567 (10)0.0461 (8)0.0025 (8)0.0061 (8)0.0055 (7)
O40.0724 (10)0.1111 (13)0.0798 (10)0.0147 (9)0.0259 (8)0.0273 (9)
C110.0526 (10)0.0588 (10)0.0517 (9)0.0012 (8)0.0033 (7)0.0002 (7)
C170.0596 (10)0.0636 (11)0.0506 (9)0.0218 (8)0.0057 (7)0.0065 (8)
C150.0836 (14)0.0755 (13)0.0480 (9)0.0017 (11)0.0080 (9)0.0067 (9)
C160.0667 (14)0.1017 (19)0.1129 (19)0.0057 (13)0.0293 (13)0.0068 (16)
Geometric parameters (Å, º) top
O1—C11.3731 (18)O3—C151.411 (2)
O1—H'0.88 (2)C10—C111.390 (2)
O2—C141.3673 (19)C10—H10A0.9300
O2—H''0.98 (3)C2—C31.383 (2)
C6—C51.382 (2)C2—H2A0.9300
C6—C11.400 (2)C14—C131.385 (2)
C6—C71.5058 (19)C3—H3A0.9300
N—C171.459 (2)C13—C121.372 (3)
N—C81.4726 (17)C13—H13A0.9300
N—C71.4714 (17)C12—C111.376 (3)
C1—C21.379 (2)C12—H12A0.9300
C7—H7A0.9700O4—C161.361 (3)
C7—H7B0.9700O4—C111.373 (2)
C8—C91.512 (2)C17—H17A0.9600
C8—H8A0.9700C17—H17B0.9600
C8—H8B0.9700C17—H17C0.9600
C9—C101.392 (2)C15—H15A0.9600
C9—C141.396 (2)C15—H15B0.9600
C5—C41.390 (2)C15—H15C0.9600
C5—H5A0.9300C16—H16A0.9600
C4—O31.3754 (19)C16—H16B0.9600
C4—C31.383 (2)C16—H16C0.9600
C1—O1—H'105.3 (14)C1—C2—H2A119.5
C14—O2—H''105.9 (16)C3—C2—H2A119.5
C5—C6—C1118.17 (13)O2—C14—C13119.18 (14)
C5—C6—C7120.97 (13)O2—C14—C9120.23 (14)
C1—C6—C7120.86 (13)C13—C14—C9120.59 (15)
C17—N—C8110.81 (12)C2—C3—C4119.39 (14)
C17—N—C7111.38 (12)C2—C3—H3A120.3
C8—N—C7111.83 (11)C4—C3—H3A120.3
O1—C1—C2122.48 (14)C12—C13—C14120.02 (16)
O1—C1—C6117.40 (13)C12—C13—H13A120.0
C2—C1—C6120.12 (14)C14—C13—H13A120.0
N—C7—C6111.97 (11)C13—C12—C11120.42 (16)
N—C7—H7A109.2C13—C12—H12A119.8
C6—C7—H7A109.2C11—C12—H12A119.8
N—C7—H7B109.2C16—O4—C11119.14 (17)
C6—C7—H7B109.2C12—C11—O4115.80 (16)
H7A—C7—H7B107.9C12—C11—C10120.00 (16)
N—C8—C9110.78 (12)O4—C11—C10124.19 (17)
N—C8—H8A109.5N—C17—H17A109.5
C9—C8—H8A109.5N—C17—H17B109.5
N—C8—H8B109.5H17A—C17—H17B109.5
C9—C8—H8B109.5N—C17—H17C109.5
H8A—C8—H8B108.1H17A—C17—H17C109.5
C10—C9—C14118.55 (14)H17B—C17—H17C109.5
C10—C9—C8122.11 (13)O3—C15—H15A109.5
C14—C9—C8119.32 (13)O3—C15—H15B109.5
C6—C5—C4121.71 (14)H15A—C15—H15B109.5
C6—C5—H5A119.1O3—C15—H15C109.5
C4—C5—H5A119.1H15A—C15—H15C109.5
O3—C4—C3124.69 (15)H15B—C15—H15C109.5
O3—C4—C5115.86 (14)O4—C16—H16A109.5
C3—C4—C5119.44 (14)O4—C16—H16B109.5
C4—O3—C15118.27 (14)H16A—C16—H16B109.5
C11—C10—C9120.40 (15)O4—C16—H16C109.5
C11—C10—H10A119.8H16A—C16—H16C109.5
C9—C10—H10A119.8H16B—C16—H16C109.5
C1—C2—C3121.09 (14)
C5—C6—C1—O1177.73 (14)C8—C9—C10—C11177.84 (15)
C7—C6—C1—O11.8 (2)O1—C1—C2—C3178.10 (15)
C5—C6—C1—C22.8 (2)C6—C1—C2—C32.5 (3)
C7—C6—C1—C2177.69 (14)C10—C9—C14—O2178.92 (14)
C17—N—C7—C663.61 (16)C8—C9—C14—O20.6 (2)
C8—N—C7—C6171.79 (11)C10—C9—C14—C130.6 (2)
C5—C6—C7—N115.64 (15)C8—C9—C14—C13178.94 (15)
C1—C6—C7—N64.88 (18)C1—C2—C3—C40.1 (3)
C17—N—C8—C975.11 (16)O3—C4—C3—C2176.96 (17)
C7—N—C8—C9159.97 (12)C5—C4—C3—C21.9 (3)
N—C8—C9—C10135.83 (14)O2—C14—C13—C12178.23 (16)
N—C8—C9—C1445.86 (18)C9—C14—C13—C121.3 (3)
C1—C6—C5—C40.8 (2)C14—C13—C12—C110.9 (3)
C7—C6—C5—C4179.69 (15)C13—C12—C11—O4179.35 (18)
C6—C5—C4—O3177.44 (15)C13—C12—C11—C100.2 (3)
C6—C5—C4—C31.6 (2)C16—O4—C11—C12166.6 (2)
C3—C4—O3—C159.2 (3)C16—O4—C11—C1014.2 (3)
C5—C4—O3—C15171.85 (17)C9—C10—C11—C120.8 (3)
C14—C9—C10—C110.5 (2)C9—C10—C11—O4179.97 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H···N0.98 (3)1.78 (3)2.6679 (16)149 (2)
O1—H···O2i0.88 (3)1.89 (3)2.7550 (16)169 (2)
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC17H21NO4
Mr303.35
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)13.3384 (9), 8.5634 (5), 14.1021 (8)
β (°) 99.340 (2)
V3)1589.42 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.54 × 0.54 × 0.28
Data collection
DiffractometerSiemens P4
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8022, 3649, 2711
Rint0.020
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.160, 1.03
No. of reflections3649
No. of parameters207
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.21

Computer programs: XSCANS (Siemens, 1992), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H''···N0.98 (3)1.78 (3)2.6679 (16)149 (2)
O1—H'···O2i0.88 (3)1.89 (3)2.7550 (16)169 (2)
Symmetry code: (i) x+1, y, z+1.
 

Acknowledgements

This work was supported by the Thailand Research Fund (grant No. MRG5480046). The authors would like to thank the Department of Chemistry, Faculty of Science, Kasetsart University, for partial support.

References

First citationLaobuthee, A., Ishida, H. & Chirachanchai, S. (2003). J. Incl. Phenom. Macrocycl. Chem. 47, 179–185.  Web of Science CrossRef CAS Google Scholar
First citationRungsimanon, T., Laobuthee, A., Miyata, M. & Chirachanchai, S. (2008). J. Incl. Phenom. Macrocycl. Chem. 62, 333–338.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiemens (1992). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar
First citationVeranitisagul, C., Kaewvilai, A., Sangngern, S., Wattanathana, W., Suramitr, S., Koonsaeng, N. & Laobuthee, A. (2011). Int. J. Mol. Sci. 12, 4365–4377.  Web of Science CrossRef CAS PubMed Google Scholar

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