[2,5-Bis(di­propyl­amino)-4-(hy­droxy­meth­yl)phen­yl]methanol

Schmitt, V.; Holzmann, G.; Schollmeyer, D.; Detert, H.

doi:10.1107/S2414314621004430

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 4| April 2021| x210443

https://doi.org/10.1107/S2414314621004430

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[2,5-Bis(dipropylamino)-4-(hydroxymethyl)phenyl]methanol

Volker Schmitt,^a Gideon Holzmann,^a Dieter Schollmeyer ^a and Heiner Detert ^a ^*

^aUniversity of Mainz, Institut for Organic Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 21 April 2021; accepted 26 April 2021; online 30 April 2021)

The centrosymmetric title compound, C₂₂H₃₆N₂O₂, was prepared in five steps from diethyl succinate. The dipropylamino groups are almost orthogonal to the central phenylenedimethanol ring [dihedral angle = 87.62 (9)°]. In the crystal, the molecules are connected by O—H⋯N hydrogen bonds, forming (101) layers separated by the propyl chains.

Keywords: crystal structure; phenylenediamine; alcohol; hydrogen bond.

CCDC reference: 2080018

Structure description

In a project focusing on acidochromic oligophenylenevinylenes (Detert et al., 2004 ; Detert & Sugiono, 2004 , 2005 ), the title compound, C₂₂H₃₆N₂O₂, was prepared as an intermediate for fluorophores with a central p-aminoaniline unit (Detert & Schmitt, 2004 , 2006 ; Schmitt et al., 2008 ).

The complete molecule is generated by a crystallographic centre of symmetry (Fig. 1) and two centrosymmetric molecules occupy the monoclinic unit cell. The molecules are composed of an almost planar aromatic ring flanked by prolate dipropylamino groups. The mean planes of the ring and the dipropylamino unit enclose a dihedral angle of 87.62 (9)°. This orientation and torsion angles of −118.97 (11)° (C1—C2—N1—C4) and 0.8 (2)° (O1—C10—C1—C3_a) lead to an H-shape for the molecule.

Figure 1
The molecular structure with displacement ellipsoids drawn at the 50% probability level. Symmetry code: (a) 1 − x, 1 − y, −z.

In the extended structure, slightly bent O—H⋯N hydrogen bonds (Table 1, Fig. 2) connect each molecule with four neighbours, thus forming a slightly undulating network with an angle of 19.9° between the mean planes of the aromatic rings of adjacent molecules. This network lies parallel to (101) and the propyl groups act as spacers between the planes.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.88 (2)	2.05 (2)	2.9269 (13)	171.7 (18)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Partial packing diagram viewed along the b-axis direction. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

The title compound was prepared from succinoyl succinate (Fehling, 1844 ) via condensation with propyl amine (Liebermann, 1914 ; Ulbricht et al., 1979 ), refluxing of the diamine with propionyl chloride for 3 h followed by aqueous work-up and recrystallization of the diamide from toluene solution with ca 10% ethyl acetate. The amide (14 g, 0.033 mol) was added slowly to a stirred and boiling suspension of lithium aluminium hydride (3.8 g, 0.1 mol) in 200 ml of ether. After refluxing for 3 h, excess hydride was destroyed by addition of first ethyl acetate, and then aqueous sodium hydroxide (40%) to the stirred solution until clotting occurred. Suction filtration and digesting of the filter cake with ether, and washing of the combined organic phases with brine gave, after concentration and crystallization, 2.4 g (22%) of the diamine. Recrystallization from acetonitrile solution resulted in 2.4 g (22%) of slightly yellowish cuboid crystals with m.p. = 400–401 K. ¹H-NMR (400 MHz, CDCl₃): 6.93 (s, 2 H ar); 4.75 (s, 4 H, benzylic), 2.83 (m, 8 H, N—CH2); 1.45 (m, 8 H), 0.85 (t, 12 H, CH₃); ¹³C-NMR (100 MHz, CDCl₃) 146.2 (C-2,5), 136.2 (C-1,4), 122.2 (C3,6), 64.8 (CH₂OH), 57.0 (NCH₂), 20.3 (CH₂), 11.5 (CH₃); FD—MS: m/z = 336.2 (100%, M⁺); IR (CDCl₃, cm⁻¹): 3370, 2960, 2940, 2870, 1630, 1500, 1455, 1410, 1285, 1255, 1140, 1055.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were located in difference Fourier maps and refined with isotropic displacement parameters.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₃₆N₂O₂
M_r	336.51
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	8.2294 (4), 8.4573 (5), 14.0115 (7)
β (°)	93.974 (4)
V (Å³)	972.83 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.25 × 0.20 × 0.16

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5278, 2318, 1995
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.112, 1.05
No. of reflections	2318
No. of parameters	172
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.16
Computer programs: X-AREA WinXpose, Recipe and Integrate (Stoe & Cie, 2019 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2080018

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314621004430/hb4382sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621004430/hb4382Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621004430/hb4382Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA WinXpose 2.0.22.0 (Stoe & Cie, 2019); cell refinement: X-AREA Recipe 1.36.0.0 (Stoe & Cie, 2019); data reduction: X-AREA Integrate 1.77.0.0 (Stoe & Cie, 2019); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020).

[2,5-Bis(dipropylamino)-4-(hydroxymethyl)phenyl]methanol top

Crystal data top

C₂₀H₃₆N₂O₂	F(000) = 372
M_r = 336.51	D_x = 1.149 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.2294 (4) Å	Cell parameters from 7030 reflections
b = 8.4573 (5) Å	θ = 2.4–28.4°
c = 14.0115 (7) Å	µ = 0.07 mm⁻¹
β = 93.974 (4)°	T = 120 K
V = 972.83 (9) Å³	Block, colourless
Z = 2	0.25 × 0.20 × 0.16 mm

Data collection top

STOE IPDS 2T diffractometer	1995 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	R_int = 0.019
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.9°, θ_min = 2.8°
rotation method, ω scans	h = −9→10
5278 measured reflections	k = −11→11
2318 independent reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	All H-atom parameters refined
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0491P)² + 0.4938P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2318 reflections	Δρ_max = 0.43 e Å⁻³
172 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O1	0.65711 (12)	0.27293 (10)	0.20873 (7)	0.0244 (2)
H1	0.717 (3)	0.257 (2)	0.2627 (16)	0.046 (5)*
N1	0.65180 (12)	0.75248 (11)	0.10757 (7)	0.0148 (2)
C1	0.57794 (13)	0.47022 (13)	0.09097 (8)	0.0146 (2)
C2	0.57352 (13)	0.62308 (13)	0.05321 (8)	0.0141 (2)
C3	0.49620 (14)	0.65103 (13)	−0.03682 (8)	0.0151 (2)
H3	0.4942 (17)	0.7560 (16)	−0.0625 (10)	0.014 (3)*
C4	0.53162 (15)	0.87545 (14)	0.12965 (8)	0.0179 (2)
H4A	0.4663 (18)	0.9151 (18)	0.0694 (10)	0.018 (2)*
H4B	0.5946 (18)	0.9662 (18)	0.1557 (10)	0.018 (2)*
C5	0.41498 (18)	0.81758 (17)	0.20128 (10)	0.0268 (3)
H5A	0.478 (2)	0.779 (2)	0.2577 (13)	0.033 (3)*
H5B	0.354 (2)	0.728 (2)	0.1733 (13)	0.033 (3)*
C6	0.3000 (2)	0.9476 (2)	0.23025 (12)	0.0369 (4)
H6A	0.227 (3)	0.908 (3)	0.2782 (15)	0.053 (3)*
H6B	0.231 (3)	0.985 (2)	0.1760 (16)	0.053 (3)*
H6C	0.365 (3)	1.039 (3)	0.2574 (15)	0.053 (3)*
C7	0.78539 (15)	0.82069 (14)	0.05542 (8)	0.0186 (3)
H7A	0.8328 (19)	0.9104 (19)	0.0947 (10)	0.020 (3)*
H7B	0.7429 (18)	0.8668 (17)	−0.0069 (11)	0.020 (3)*
C8	0.91847 (17)	0.70094 (17)	0.03952 (11)	0.0285 (3)
H8A	0.870 (2)	0.613 (2)	0.0016 (13)	0.042 (4)*
H8B	0.959 (2)	0.658 (2)	0.1023 (14)	0.042 (4)*
C9	1.05723 (19)	0.77308 (19)	−0.01183 (12)	0.0327 (3)
H9A	1.142 (3)	0.698 (2)	−0.0227 (14)	0.045 (3)*
H9B	1.106 (2)	0.864 (2)	0.0248 (14)	0.045 (3)*
H9C	1.013 (2)	0.821 (2)	−0.0742 (15)	0.045 (3)*
C10	0.66429 (16)	0.43700 (14)	0.18745 (8)	0.0186 (3)
H10A	0.777 (2)	0.4729 (19)	0.1861 (11)	0.024 (3)*
H10B	0.6141 (19)	0.4995 (19)	0.2383 (11)	0.024 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0380 (5)	0.0142 (4)	0.0190 (4)	−0.0034 (4)	−0.0123 (4)	0.0048 (3)
N1	0.0182 (5)	0.0116 (4)	0.0141 (4)	−0.0019 (4)	−0.0016 (3)	−0.0011 (3)
C1	0.0168 (5)	0.0139 (5)	0.0129 (5)	0.0001 (4)	−0.0010 (4)	0.0010 (4)
C2	0.0160 (5)	0.0127 (5)	0.0134 (5)	−0.0011 (4)	−0.0008 (4)	−0.0015 (4)
C3	0.0190 (5)	0.0117 (5)	0.0144 (5)	−0.0004 (4)	−0.0012 (4)	0.0015 (4)
C4	0.0229 (6)	0.0135 (5)	0.0170 (5)	0.0012 (4)	−0.0019 (4)	−0.0015 (4)
C5	0.0304 (7)	0.0249 (7)	0.0260 (6)	0.0042 (5)	0.0079 (5)	0.0005 (5)
C6	0.0368 (8)	0.0409 (9)	0.0340 (8)	0.0107 (7)	0.0087 (7)	−0.0052 (7)
C7	0.0211 (6)	0.0166 (5)	0.0177 (5)	−0.0042 (4)	−0.0005 (4)	0.0005 (4)
C8	0.0241 (6)	0.0219 (6)	0.0401 (8)	−0.0012 (5)	0.0062 (6)	0.0024 (6)
C9	0.0269 (7)	0.0320 (8)	0.0404 (8)	−0.0047 (6)	0.0098 (6)	−0.0032 (6)
C10	0.0269 (6)	0.0126 (5)	0.0152 (5)	−0.0020 (5)	−0.0062 (4)	0.0016 (4)

Geometric parameters (Å, º) top

O1—C10	1.4214 (14)	C5—H5B	0.977 (18)
O1—H1	0.88 (2)	C6—H6A	0.99 (2)
N1—C2	1.4577 (13)	C6—H6B	0.97 (2)
N1—C7	1.4787 (15)	C6—H6C	1.00 (2)
N1—C4	1.4825 (15)	C7—C8	1.5194 (18)
C1—C3ⁱ	1.3912 (15)	C7—H7A	1.001 (16)
C1—C2	1.3964 (15)	C7—H7B	0.997 (15)
C1—C10	1.5094 (15)	C8—C9	1.5191 (19)
C2—C3	1.3931 (15)	C8—H8A	0.99 (2)
C3—H3	0.958 (14)	C8—H8B	0.99 (2)
C4—C5	1.5171 (18)	C9—H9A	0.97 (2)
C4—H4A	1.025 (15)	C9—H9B	0.99 (2)
C4—H4B	0.982 (15)	C9—H9C	1.01 (2)
C5—C6	1.524 (2)	C10—H10A	0.980 (16)
C5—H5A	0.970 (19)	C10—H10B	0.999 (16)

C10—O1—H1	107.6 (13)	C5—C6—H6C	109.6 (12)
C2—N1—C7	110.57 (9)	H6A—C6—H6C	109.8 (17)
C2—N1—C4	111.02 (9)	H6B—C6—H6C	108.3 (17)
C7—N1—C4	111.04 (9)	N1—C7—C8	112.37 (10)
C3ⁱ—C1—C2	118.48 (10)	N1—C7—H7A	107.4 (9)
C3ⁱ—C1—C10	120.84 (10)	C8—C7—H7A	109.2 (9)
C2—C1—C10	120.66 (10)	N1—C7—H7B	110.9 (9)
C3—C2—C1	119.90 (10)	C8—C7—H7B	110.2 (9)
C3—C2—N1	120.22 (10)	H7A—C7—H7B	106.6 (12)
C1—C2—N1	119.88 (9)	C9—C8—C7	112.02 (12)
C1ⁱ—C3—C2	121.62 (10)	C9—C8—H8A	109.9 (11)
C1ⁱ—C3—H3	118.9 (8)	C7—C8—H8A	108.2 (11)
C2—C3—H3	119.5 (8)	C9—C8—H8B	110.7 (11)
N1—C4—C5	111.94 (10)	C7—C8—H8B	108.4 (11)
N1—C4—H4A	112.2 (8)	H8A—C8—H8B	107.5 (15)
C5—C4—H4A	109.3 (8)	C8—C9—H9A	112.8 (12)
N1—C4—H4B	106.4 (9)	C8—C9—H9B	111.0 (11)
C5—C4—H4B	110.4 (9)	H9A—C9—H9B	108.4 (16)
H4A—C4—H4B	106.4 (12)	C8—C9—H9C	109.4 (11)
C4—C5—C6	112.13 (12)	H9A—C9—H9C	110.4 (16)
C4—C5—H5A	108.8 (10)	H9B—C9—H9C	104.5 (16)
C6—C5—H5A	109.3 (10)	O1—C10—C1	110.23 (9)
C4—C5—H5B	108.5 (10)	O1—C10—H10A	111.1 (9)
C6—C5—H5B	110.8 (10)	C1—C10—H10A	108.3 (9)
H5A—C5—H5B	107.2 (15)	O1—C10—H10B	110.0 (9)
C5—C6—H6A	110.6 (13)	C1—C10—H10B	110.4 (9)
C5—C6—H6B	111.6 (12)	H10A—C10—H10B	106.9 (13)
H6A—C6—H6B	106.9 (17)

C3ⁱ—C1—C2—C3	−0.09 (18)	N1—C2—C3—C1ⁱ	179.23 (10)
C10—C1—C2—C3	178.66 (11)	C2—N1—C4—C5	69.20 (12)
C3ⁱ—C1—C2—N1	−179.23 (10)	C7—N1—C4—C5	−167.35 (10)
C10—C1—C2—N1	−0.48 (16)	N1—C4—C5—C6	175.43 (12)
C7—N1—C2—C3	−61.82 (13)	C2—N1—C7—C8	−61.45 (13)
C4—N1—C2—C3	61.89 (13)	C4—N1—C7—C8	174.85 (10)
C7—N1—C2—C1	117.32 (11)	N1—C7—C8—C9	−178.53 (11)
C4—N1—C2—C1	−118.97 (11)	C3ⁱ—C1—C10—O1	0.79 (16)
C1—C2—C3—C1ⁱ	0.09 (19)	C2—C1—C10—O1	−177.92 (10)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱⁱ	0.88 (2)	2.05 (2)	2.9269 (13)	171.7 (18)

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

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