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

Veranitisagul, C.; Kaewvilai, A.; Duangthongyou, T.; Koonsaeng, N.; Laobuthee, A.

doi:10.1107/S1600536812026694

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2139

https://doi.org/10.1107/S1600536812026694

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

Chatchai Veranitisagul,^a Attaphon Kaewvilai,^b Tanwawan Duangthongyou,^c Nattamon Koonsaeng ^c and Apirat Laobuthee ^b ^*

^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 ). 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

Crystal data

C₁₇H₂₁NO₄
M_r = 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)
R_int = 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
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: XSCANS; data reduction: XSCANS; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812026694/nc2280sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026694/nc2280Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812026694/nc2280Isup3.cml

checkCIF report

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.

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

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

C₁₇H₂₁NO₄	F(000) = 648
M_r = 303.35	D_x = 1.268 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.3384 (9) Å	Cell parameters from 3446 reflections
b = 8.5634 (5) Å	θ = 2.8–27.3°
c = 14.1021 (8) Å	µ = 0.09 mm⁻¹
β = 99.340 (2)°	T = 296 K
V = 1589.42 (17) Å³	Block, colourless
Z = 4	0.54 × 0.54 × 0.28 mm

Data collection top

Siemens P4 diffractometer	2711 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 27.5°, θ_min = 1.6°
ω scans	h = −17→16
8022 measured reflections	k = −11→8
3649 independent reflections	l = −18→12

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0949P)² + 0.2159P] where P = (F_o² + 2F_c²)/3
3649 reflections	(Δ/σ)_max < 0.001
207 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₇H₂₁NO₄	V = 1589.42 (17) Å³
M_r = 303.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.3384 (9) Å	µ = 0.09 mm⁻¹
b = 8.5634 (5) Å	T = 296 K
c = 14.1021 (8) Å	0.54 × 0.54 × 0.28 mm
β = 99.340 (2)°

Data collection top

Siemens P4 diffractometer	2711 reflections with I > 2σ(I)
8022 measured reflections	R_int = 0.020
3649 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.30 e Å⁻³
3649 reflections	Δρ_min = −0.21 e Å⁻³
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

	x	y	z	U_iso*/U_eq
O1	0.45389 (9)	0.03013 (15)	0.59042 (8)	0.0530 (3)
O2	0.34001 (8)	0.00867 (16)	0.40230 (8)	0.0589 (4)
C6	0.33681 (11)	0.08049 (17)	0.69636 (10)	0.0404 (3)
N	0.22980 (9)	0.08969 (14)	0.53635 (8)	0.0377 (3)
C1	0.42488 (11)	0.00508 (18)	0.67825 (10)	0.0418 (3)
C7	0.27517 (11)	0.18108 (17)	0.62086 (10)	0.0429 (3)
H7A	0.2216	0.2321	0.6483	0.051*
H7B	0.3185	0.2616	0.6009	0.051*
C8	0.18208 (11)	0.19071 (18)	0.45720 (10)	0.0435 (3)
H8A	0.2238	0.2826	0.4537	0.052*
H8B	0.1161	0.2248	0.4696	0.052*
C9	0.16962 (11)	0.10444 (17)	0.36246 (10)	0.0404 (3)
C5	0.30850 (12)	0.0610 (2)	0.78563 (10)	0.0469 (4)
H5A	0.2507	0.1115	0.7990	0.056*
C4	0.36425 (13)	−0.0320 (2)	0.85596 (11)	0.0494 (4)
O3	0.33023 (11)	−0.03631 (18)	0.94292 (9)	0.0712 (4)
C10	0.08049 (12)	0.1124 (2)	0.29590 (11)	0.0492 (4)
H10A	0.0255	0.1694	0.3102	0.059*
C2	0.47847 (12)	−0.0911 (2)	0.74694 (12)	0.0504 (4)
H2A	0.5354	−0.1438	0.7333	0.061*
C14	0.25065 (12)	0.01707 (19)	0.33939 (10)	0.0443 (4)
C3	0.44897 (12)	−0.1103 (2)	0.83577 (12)	0.0515 (4)
H3A	0.4858	−0.1754	0.8815	0.062*
C13	0.24199 (14)	−0.0611 (2)	0.25243 (12)	0.0543 (4)
H13A	0.2959	−0.1207	0.2382	0.065*
C12	0.15387 (15)	−0.0506 (2)	0.18727 (12)	0.0579 (4)
H12A	0.1487	−0.1020	0.1286	0.069*
O4	−0.01176 (13)	0.0372 (2)	0.13858 (11)	0.0920 (5)
C11	0.07316 (13)	0.0356 (2)	0.20820 (12)	0.0557 (4)
C17	0.15734 (14)	−0.0249 (2)	0.56118 (13)	0.0583 (5)
H17A	0.1291	−0.0826	0.5048	0.088*
H17B	0.1038	0.0279	0.5863	0.088*
H17C	0.1914	−0.0953	0.6088	0.088*
C15	0.37548 (17)	−0.1441 (3)	1.01268 (12)	0.0693 (5)
H15A	0.3448	−0.1346	1.0694	0.104*
H15B	0.4469	−0.1228	1.0284	0.104*
H15C	0.3656	−0.2482	0.9877	0.104*
C16	−0.08619 (18)	0.1436 (3)	0.14472 (19)	0.0986 (8)
H16A	−0.1401	0.1305	0.0913	0.148*
H16B	−0.0588	0.2471	0.1435	0.148*
H16C	−0.1122	0.1283	0.2036	0.148*
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

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0356 (6)	0.0755 (8)	0.0493 (6)	0.0063 (5)	0.0109 (5)	0.0030 (5)
O2	0.0376 (6)	0.0946 (10)	0.0453 (6)	0.0165 (6)	0.0090 (5)	0.0014 (6)
C6	0.0375 (7)	0.0397 (7)	0.0427 (7)	0.0025 (6)	0.0029 (6)	−0.0076 (6)
N	0.0360 (6)	0.0384 (6)	0.0387 (6)	0.0005 (5)	0.0058 (5)	0.0017 (5)
C1	0.0344 (7)	0.0474 (8)	0.0435 (7)	−0.0011 (6)	0.0055 (6)	−0.0052 (6)
C7	0.0419 (8)	0.0393 (8)	0.0467 (7)	0.0051 (6)	0.0050 (6)	−0.0050 (6)
C8	0.0412 (7)	0.0439 (8)	0.0450 (7)	0.0074 (6)	0.0059 (6)	0.0043 (6)
C9	0.0383 (7)	0.0410 (8)	0.0420 (7)	0.0002 (6)	0.0069 (6)	0.0076 (6)
C5	0.0448 (8)	0.0510 (9)	0.0449 (8)	0.0096 (7)	0.0074 (6)	−0.0088 (6)
C4	0.0500 (9)	0.0577 (10)	0.0404 (7)	0.0045 (7)	0.0070 (6)	−0.0038 (7)
O3	0.0790 (9)	0.0930 (10)	0.0435 (6)	0.0266 (8)	0.0159 (6)	0.0074 (6)
C10	0.0409 (8)	0.0513 (9)	0.0538 (8)	0.0043 (7)	0.0033 (6)	0.0027 (7)
C2	0.0381 (8)	0.0556 (9)	0.0578 (9)	0.0102 (7)	0.0083 (7)	0.0000 (7)
C14	0.0393 (8)	0.0524 (9)	0.0422 (7)	0.0031 (6)	0.0095 (6)	0.0089 (6)
C3	0.0467 (9)	0.0544 (9)	0.0511 (8)	0.0087 (7)	0.0009 (7)	0.0045 (7)
C13	0.0572 (10)	0.0590 (10)	0.0490 (8)	0.0108 (8)	0.0147 (7)	0.0017 (7)
C12	0.0697 (12)	0.0567 (10)	0.0461 (8)	0.0025 (8)	0.0061 (8)	−0.0055 (7)
O4	0.0724 (10)	0.1111 (13)	0.0798 (10)	0.0147 (9)	−0.0259 (8)	−0.0273 (9)
C11	0.0526 (10)	0.0588 (10)	0.0517 (9)	−0.0012 (8)	−0.0033 (7)	−0.0002 (7)
C17	0.0596 (10)	0.0636 (11)	0.0506 (9)	−0.0218 (8)	0.0057 (7)	0.0065 (8)
C15	0.0836 (14)	0.0755 (13)	0.0480 (9)	−0.0017 (11)	0.0080 (9)	0.0067 (9)
C16	0.0667 (14)	0.1017 (19)	0.1129 (19)	0.0057 (13)	−0.0293 (13)	0.0068 (16)

Geometric parameters (Å, º) top

O1—C1	1.3731 (18)	O3—C15	1.411 (2)
O1—H'	0.88 (2)	C10—C11	1.390 (2)
O2—C14	1.3673 (19)	C10—H10A	0.9300
O2—H''	0.98 (3)	C2—C3	1.383 (2)
C6—C5	1.382 (2)	C2—H2A	0.9300
C6—C1	1.400 (2)	C14—C13	1.385 (2)
C6—C7	1.5058 (19)	C3—H3A	0.9300
N—C17	1.459 (2)	C13—C12	1.372 (3)
N—C8	1.4726 (17)	C13—H13A	0.9300
N—C7	1.4714 (17)	C12—C11	1.376 (3)
C1—C2	1.379 (2)	C12—H12A	0.9300
C7—H7A	0.9700	O4—C16	1.361 (3)
C7—H7B	0.9700	O4—C11	1.373 (2)
C8—C9	1.512 (2)	C17—H17A	0.9600
C8—H8A	0.9700	C17—H17B	0.9600
C8—H8B	0.9700	C17—H17C	0.9600
C9—C10	1.392 (2)	C15—H15A	0.9600
C9—C14	1.396 (2)	C15—H15B	0.9600
C5—C4	1.390 (2)	C15—H15C	0.9600
C5—H5A	0.9300	C16—H16A	0.9600
C4—O3	1.3754 (19)	C16—H16B	0.9600
C4—C3	1.383 (2)	C16—H16C	0.9600

C1—O1—H'	105.3 (14)	C1—C2—H2A	119.5
C14—O2—H''	105.9 (16)	C3—C2—H2A	119.5
C5—C6—C1	118.17 (13)	O2—C14—C13	119.18 (14)
C5—C6—C7	120.97 (13)	O2—C14—C9	120.23 (14)
C1—C6—C7	120.86 (13)	C13—C14—C9	120.59 (15)
C17—N—C8	110.81 (12)	C2—C3—C4	119.39 (14)
C17—N—C7	111.38 (12)	C2—C3—H3A	120.3
C8—N—C7	111.83 (11)	C4—C3—H3A	120.3
O1—C1—C2	122.48 (14)	C12—C13—C14	120.02 (16)
O1—C1—C6	117.40 (13)	C12—C13—H13A	120.0
C2—C1—C6	120.12 (14)	C14—C13—H13A	120.0
N—C7—C6	111.97 (11)	C13—C12—C11	120.42 (16)
N—C7—H7A	109.2	C13—C12—H12A	119.8
C6—C7—H7A	109.2	C11—C12—H12A	119.8
N—C7—H7B	109.2	C16—O4—C11	119.14 (17)
C6—C7—H7B	109.2	C12—C11—O4	115.80 (16)
H7A—C7—H7B	107.9	C12—C11—C10	120.00 (16)
N—C8—C9	110.78 (12)	O4—C11—C10	124.19 (17)
N—C8—H8A	109.5	N—C17—H17A	109.5
C9—C8—H8A	109.5	N—C17—H17B	109.5
N—C8—H8B	109.5	H17A—C17—H17B	109.5
C9—C8—H8B	109.5	N—C17—H17C	109.5
H8A—C8—H8B	108.1	H17A—C17—H17C	109.5
C10—C9—C14	118.55 (14)	H17B—C17—H17C	109.5
C10—C9—C8	122.11 (13)	O3—C15—H15A	109.5
C14—C9—C8	119.32 (13)	O3—C15—H15B	109.5
C6—C5—C4	121.71 (14)	H15A—C15—H15B	109.5
C6—C5—H5A	119.1	O3—C15—H15C	109.5
C4—C5—H5A	119.1	H15A—C15—H15C	109.5
O3—C4—C3	124.69 (15)	H15B—C15—H15C	109.5
O3—C4—C5	115.86 (14)	O4—C16—H16A	109.5
C3—C4—C5	119.44 (14)	O4—C16—H16B	109.5
C4—O3—C15	118.27 (14)	H16A—C16—H16B	109.5
C11—C10—C9	120.40 (15)	O4—C16—H16C	109.5
C11—C10—H10A	119.8	H16A—C16—H16C	109.5
C9—C10—H10A	119.8	H16B—C16—H16C	109.5
C1—C2—C3	121.09 (14)

C5—C6—C1—O1	−177.73 (14)	C8—C9—C10—C11	177.84 (15)
C7—C6—C1—O1	1.8 (2)	O1—C1—C2—C3	178.10 (15)
C5—C6—C1—C2	2.8 (2)	C6—C1—C2—C3	−2.5 (3)
C7—C6—C1—C2	−177.69 (14)	C10—C9—C14—O2	178.92 (14)
C17—N—C7—C6	63.61 (16)	C8—C9—C14—O2	0.6 (2)
C8—N—C7—C6	−171.79 (11)	C10—C9—C14—C13	−0.6 (2)
C5—C6—C7—N	−115.64 (15)	C8—C9—C14—C13	−178.94 (15)
C1—C6—C7—N	64.88 (18)	C1—C2—C3—C4	0.1 (3)
C17—N—C8—C9	−75.11 (16)	O3—C4—C3—C2	−176.96 (17)
C7—N—C8—C9	159.97 (12)	C5—C4—C3—C2	1.9 (3)
N—C8—C9—C10	135.83 (14)	O2—C14—C13—C12	−178.23 (16)
N—C8—C9—C14	−45.86 (18)	C9—C14—C13—C12	1.3 (3)
C1—C6—C5—C4	−0.8 (2)	C14—C13—C12—C11	−0.9 (3)
C7—C6—C5—C4	179.69 (15)	C13—C12—C11—O4	−179.35 (18)
C6—C5—C4—O3	177.44 (15)	C13—C12—C11—C10	−0.2 (3)
C6—C5—C4—C3	−1.6 (2)	C16—O4—C11—C12	−166.6 (2)
C3—C4—O3—C15	−9.2 (3)	C16—O4—C11—C10	14.2 (3)
C5—C4—O3—C15	171.85 (17)	C9—C10—C11—C12	0.8 (3)
C14—C9—C10—C11	−0.5 (2)	C9—C10—C11—O4	179.97 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₁NO₄
M_r	303.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.3384 (9), 8.5634 (5), 14.1021 (8)
β (°)	99.340 (2)
V (Å³)	1589.42 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.54 × 0.54 × 0.28

Data collection
Diffractometer	Siemens P4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8022, 3649, 2711
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.160, 1.03
No. of reflections	3649
No. of parameters	207
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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.

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.

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