4-{[1-(4-Bromo­phen­yl)eth­yl]amino­meth­yl}phenol

Gonzalez Nieves, K.

doi:10.1107/S1600536811028339

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2110

doi:10.1107/S1600536811028339

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4-{[1-(4-Bromophenyl)ethyl]aminomethyl}phenol

Karilys Gonzalez Nieves ^a ^*

^aDepartment of Chemistry, University of Puerto Rico, San Juan, PR 00931, Puerto Rico
^*Correspondence e-mail: karilysgn@yahoo.com

(Received 4 June 2011; accepted 14 July 2011; online 23 July 2011)

The title compound, C₁₅H₁₆BrNO, obtained from a two-step reaction, was prepared for use in transition metal chemistry as a phenolic ligand with bulky substituents. Intermolecular N—H⋯O and O—H⋯N hydrogen bonds are present in the crystal structure.

Related literature

For chirality induction in metal complexes, see: Fan et al. (2010 ); Amendola et al. (2010 ). For imine reduction, see: Menta & Prabhakar (1995 ).

Experimental

Crystal data

C₁₅H₁₆BrNO
M_r = 306.20
Monoclinic, P 2₁ /c
a = 12.1753 (10) Å
b = 8.1939 (7) Å
c = 14.0326 (11) Å
β = 93.333 (1)°
V = 1397.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.93 mm⁻¹
T = 296 K
0.20 × 0.16 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.592, T_max = 0.685
14961 measured reflections
3094 independent reflections
2119 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.077
S = 1.00
3094 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.82	2.05	2.794 (2)	150
N1—H1⋯O1ⁱⁱ	0.75 (2)	2.40 (2)	3.144 (3)	168 (2)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811028339/fy2015sup1.cif

Supporting information file. DOI: 10.1107/S1600536811028339/fy2015Isup2.cml

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028339/fy2015Isup3.hkl

checkCIF report

Comment top

The title compound was prepared to be used as a ligand in order to induce chirality in transition metal complexes in combination with other bridging ligands. Here, we report the crystal structure of racemic 4-((1-(4-bromophenyl)ethylamino)methyl)phenol. In the crystal structure (Fig. 4), intermolecular hydrogen bonding was observed between N1—H1···O1 and O1—H1A···N1 (Table 1).

Related literature top

For chirality induction in metal complexes, see: Fan et al. (2010); Amendola et al. (2010). For imine reduction, see: Menta & Prabhakar (1995).

Experimental top

An excess of racemic 4-bromo-α-methylbenzylamine (0.069 g, 0.45 mmol) was added to a solution of 4-hydroxybenzaldehyde (0.036 g, 0.29 mmol) in ethyl acetate. The solution was stirred overnight at room temperature. The solvent was removed under vacuum to obtain 4-((1-(4-bromophenyl)ethylimino)methyl)phenol as a white solid. The Schiff base was dissolved in anhydrous MeOH and an excess of NaBH₄ was added in several portions to the reaction mixture. After 24 h, water was added to the solution, and stirring was continued for two more hours. Methanol was removed under vacuum and the remaining aqueous phase was extracted three times with ethyl acetate. The combinated organic extracts were dried with magnesium sulfate, and the solvent was removed under vacuum to obtain a white solid. The product was dissolved in acetone and crystals were obtained by vapor diffusion of pentane.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

	Fig. 1. Molecular structure of compound (I) with 50% probability displacement ellipsoid for non hydrogen atoms.
	Fig. 2. Packing diagram of compound (I).
	Fig. 3. Molecular view along a axis.
	Fig. 4. Molecular structure of compound (I) with hydrogen bonding.

4-{[1-(4-Bromophenyl)ethyl]aminomethyl}phenol top

Crystal data top

C₁₅H₁₆BrNO	F(000) = 624
M_r = 306.20	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5896 reflections
a = 12.1753 (10) Å	θ = 2.3–26.2°
b = 8.1939 (7) Å	µ = 2.93 mm⁻¹
c = 14.0326 (11) Å	T = 296 K
β = 93.333 (1)°	Block, colourless
V = 1397.6 (2) Å³	0.20 × 0.16 × 0.14 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3094 independent reflections
Radiation source: fine-focus sealed tube	2119 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 27.2°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −15→15
T_min = 0.592, T_max = 0.685	k = −10→10
14961 measured reflections	l = −17→18

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.031P)² + 0.5405P] where P = (F_o² + 2F_c²)/3
3094 reflections	(Δ/σ)_max = 0.002
168 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₁₅H₁₆BrNO	V = 1397.6 (2) Å³
M_r = 306.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.1753 (10) Å	µ = 2.93 mm⁻¹
b = 8.1939 (7) Å	T = 296 K
c = 14.0326 (11) Å	0.20 × 0.16 × 0.14 mm
β = 93.333 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3094 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	2119 reflections with I > 2σ(I)
T_min = 0.592, T_max = 0.685	R_int = 0.031
14961 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.25 e Å⁻³
3094 reflections	Δρ_min = −0.40 e Å⁻³
168 parameters

Special details top

Experimental. IR (KBr cm^-1): 3448 (m), 3280 (m), 2970 (m), 2824 (m), 1613 (m, C=C), 1592 (m), 1516 (s), 1469 (m), 1373 (m), 1251 (s), 1174 (m), 1009 (s), 862 (w), 829 (s), 635 (w), 501 (w). ¹H-NMR (500 MHz, d₆-acetone) p.p.m.: 1.28–1.30 (d, 3H, CH₃), 3.44–3.52 (dd, 2H, –CH₂NH), 3.77–3.81 (m, 1H, CHCH₃), 6.75–6.77 (d, 2H, aromatic protons in the phenyl ring), 7.10–7.11 (d, 2H, aromatic protons in bromophenyl ring), 7.35–7.37 (d, 2H, aromatic protons in bromophenyl ring), 7.48–7.50 (d, 2H, aromatic protons in the phenyl ring). ¹³C-NMR (125 MHz, d₆-acetone) p.p.m.: 24.7 (CH₃CH–), 51.5 (–CH₂NH), 57.5 (–CHCH₃), 115.8 and 132.1 (aromatic carbons in the phenyl ring), 132.1 (quaternary carbon), 120.6 (quaternary carbon, Br), 129.7 and 130.1 (aromatic carbons in the bromophenyl ring), 157.1 (quaternary carbon, OH).

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
Br1	0.50613 (2)	1.10683 (4)	0.22306 (2)	0.07679 (13)
C1	0.57389 (19)	0.9552 (3)	0.14304 (16)	0.0493 (5)
C2	0.51175 (19)	0.8545 (3)	0.08329 (17)	0.0548 (6)
H2	0.4354	0.8616	0.0801	0.066*
C3	0.56405 (18)	0.7419 (3)	0.02779 (16)	0.0491 (5)
H3	0.5220	0.6728	−0.0123	0.059*
C4	0.67743 (17)	0.7301 (3)	0.03077 (15)	0.0433 (5)
C5	0.73784 (19)	0.8363 (3)	0.09060 (18)	0.0585 (6)
H5	0.8143	0.8322	0.0927	0.070*
C6	0.6869 (2)	0.9475 (3)	0.14675 (18)	0.0574 (6)
H6	0.7285	1.0170	0.1869	0.069*
C7	0.73506 (19)	0.6046 (3)	−0.02810 (15)	0.0477 (5)
H7	0.6796	0.5310	−0.0577	0.057*
C8	0.7982 (2)	0.6822 (3)	−0.10623 (18)	0.0675 (7)
H8A	0.8519	0.7565	−0.0783	0.101*
H8B	0.7481	0.7406	−0.1492	0.101*
H8C	0.8346	0.5988	−0.1406	0.101*
C9	0.75156 (18)	0.3972 (3)	0.09742 (17)	0.0533 (6)
H9A	0.7273	0.3024	0.0606	0.064*
H9B	0.6866	0.4527	0.1178	0.064*
C10	0.81988 (17)	0.3415 (3)	0.18429 (15)	0.0433 (5)
C11	0.78927 (19)	0.3829 (3)	0.27448 (17)	0.0533 (6)
H11	0.7270	0.4470	0.2805	0.064*
C12	0.8484 (2)	0.3320 (3)	0.35547 (17)	0.0567 (6)
H12	0.8266	0.3631	0.4152	0.068*
C13	0.94031 (17)	0.2344 (3)	0.34832 (16)	0.0464 (5)
C14	0.97270 (17)	0.1923 (3)	0.25915 (16)	0.0511 (6)
H14	1.0348	0.1279	0.2533	0.061*
C15	0.91298 (18)	0.2458 (3)	0.17840 (16)	0.0518 (6)
H15	0.9359	0.2168	0.1186	0.062*
N1	0.81141 (15)	0.5077 (2)	0.03586 (14)	0.0449 (4)
O1	0.99339 (13)	0.1835 (2)	0.43153 (11)	0.0617 (4)
H1A	1.0488	0.1325	0.4195	0.093*
H1	0.8475 (17)	0.456 (3)	0.0064 (14)	0.033 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0736 (2)	0.0705 (2)	0.0891 (2)	0.00063 (14)	0.02858 (15)	−0.02241 (16)
C1	0.0551 (13)	0.0417 (12)	0.0522 (13)	0.0010 (10)	0.0123 (11)	0.0010 (11)
C2	0.0435 (12)	0.0577 (15)	0.0637 (15)	−0.0006 (11)	0.0079 (11)	−0.0007 (12)
C3	0.0467 (12)	0.0487 (13)	0.0512 (13)	−0.0049 (10)	−0.0029 (10)	−0.0018 (11)
C4	0.0472 (12)	0.0412 (11)	0.0411 (12)	0.0027 (10)	−0.0006 (9)	0.0042 (10)
C5	0.0421 (12)	0.0566 (14)	0.0763 (17)	0.0020 (11)	−0.0012 (12)	−0.0133 (13)
C6	0.0556 (14)	0.0496 (13)	0.0665 (16)	−0.0027 (11)	−0.0014 (12)	−0.0107 (12)
C7	0.0506 (12)	0.0489 (12)	0.0427 (12)	0.0025 (10)	−0.0040 (10)	0.0009 (11)
C8	0.0771 (18)	0.0749 (18)	0.0510 (14)	0.0131 (15)	0.0094 (13)	0.0074 (13)
C9	0.0430 (12)	0.0539 (13)	0.0626 (15)	−0.0028 (11)	−0.0008 (11)	0.0085 (12)
C10	0.0399 (11)	0.0394 (11)	0.0506 (13)	−0.0017 (9)	0.0035 (10)	0.0084 (10)
C11	0.0475 (13)	0.0493 (13)	0.0641 (15)	0.0123 (10)	0.0108 (11)	0.0055 (12)
C12	0.0605 (15)	0.0623 (15)	0.0489 (14)	0.0114 (12)	0.0153 (12)	0.0037 (12)
C13	0.0433 (11)	0.0479 (12)	0.0483 (13)	0.0001 (10)	0.0070 (10)	0.0112 (10)
C14	0.0435 (12)	0.0584 (14)	0.0524 (14)	0.0099 (10)	0.0107 (11)	0.0078 (11)
C15	0.0477 (13)	0.0623 (15)	0.0462 (13)	0.0050 (11)	0.0091 (10)	0.0009 (11)
N1	0.0432 (10)	0.0470 (11)	0.0448 (11)	0.0061 (9)	0.0044 (9)	0.0020 (9)
O1	0.0559 (10)	0.0796 (12)	0.0501 (9)	0.0145 (9)	0.0084 (8)	0.0167 (9)

Geometric parameters (Å, º) top

Br1—C1	1.895 (2)	C9—N1	1.473 (3)
C1—C6	1.375 (3)	C9—C10	1.506 (3)
C1—C2	1.372 (3)	C9—H9A	0.9700
C2—C3	1.386 (3)	C9—H9B	0.9700
C2—H2	0.9300	C10—C11	1.382 (3)
C3—C4	1.382 (3)	C10—C15	1.384 (3)
C3—H3	0.9300	C11—C12	1.375 (3)
C4—C5	1.390 (3)	C11—H11	0.9300
C4—C7	1.516 (3)	C12—C13	1.384 (3)
C5—C6	1.376 (3)	C12—H12	0.9300
C5—H5	0.9300	C13—O1	1.366 (3)
C6—H6	0.9300	C13—C14	1.377 (3)
C7—N1	1.484 (3)	C14—C15	1.382 (3)
C7—C8	1.515 (3)	C14—H14	0.9300
C7—H7	0.9800	C15—H15	0.9300
C8—H8A	0.9600	N1—H1	0.75 (2)
C8—H8B	0.9600	O1—H1A	0.8200
C8—H8C	0.9600

C6—C1—C2	120.7 (2)	H8B—C8—H8C	109.5
C6—C1—Br1	118.46 (18)	N1—C9—C10	113.10 (18)
C2—C1—Br1	120.85 (18)	N1—C9—H9A	109.0
C1—C2—C3	119.3 (2)	C10—C9—H9A	109.0
C1—C2—H2	120.4	N1—C9—H9B	109.0
C3—C2—H2	120.4	C10—C9—H9B	109.0
C4—C3—C2	121.3 (2)	H9A—C9—H9B	107.8
C4—C3—H3	119.3	C11—C10—C15	117.3 (2)
C2—C3—H3	119.3	C11—C10—C9	120.04 (19)
C3—C4—C5	117.8 (2)	C15—C10—C9	122.6 (2)
C3—C4—C7	121.6 (2)	C12—C11—C10	121.7 (2)
C5—C4—C7	120.55 (19)	C12—C11—H11	119.1
C6—C5—C4	121.3 (2)	C10—C11—H11	119.1
C6—C5—H5	119.3	C11—C12—C13	120.2 (2)
C4—C5—H5	119.3	C11—C12—H12	119.9
C1—C6—C5	119.5 (2)	C13—C12—H12	119.9
C1—C6—H6	120.3	O1—C13—C14	123.6 (2)
C5—C6—H6	120.3	O1—C13—C12	117.3 (2)
N1—C7—C4	109.06 (17)	C14—C13—C12	119.1 (2)
N1—C7—C8	109.62 (19)	C13—C14—C15	120.1 (2)
C4—C7—C8	112.33 (19)	C13—C14—H14	120.0
N1—C7—H7	108.6	C15—C14—H14	120.0
C4—C7—H7	108.6	C10—C15—C14	121.6 (2)
C8—C7—H7	108.6	C10—C15—H15	119.2
C7—C8—H8A	109.5	C14—C15—H15	119.2
C7—C8—H8B	109.5	C9—N1—C7	111.68 (17)
H8A—C8—H8B	109.5	C9—N1—H1	107.4 (16)
C7—C8—H8C	109.5	C7—N1—H1	109.6 (16)
H8A—C8—H8C	109.5	C13—O1—H1A	109.5

C6—C1—C2—C3	1.3 (4)	N1—C9—C10—C15	−64.5 (3)
Br1—C1—C2—C3	−178.17 (17)	C15—C10—C11—C12	0.1 (3)
C1—C2—C3—C4	−0.6 (3)	C9—C10—C11—C12	178.9 (2)
C2—C3—C4—C5	−0.7 (3)	C10—C11—C12—C13	−1.0 (4)
C2—C3—C4—C7	178.6 (2)	C11—C12—C13—O1	−177.9 (2)
C3—C4—C5—C6	1.4 (4)	C11—C12—C13—C14	1.4 (4)
C7—C4—C5—C6	−178.0 (2)	O1—C13—C14—C15	178.5 (2)
C2—C1—C6—C5	−0.7 (4)	C12—C13—C14—C15	−0.8 (4)
Br1—C1—C6—C5	178.81 (19)	C11—C10—C15—C14	0.5 (3)
C4—C5—C6—C1	−0.7 (4)	C9—C10—C15—C14	−178.2 (2)
C3—C4—C7—N1	−126.1 (2)	C13—C14—C15—C10	−0.2 (4)
C5—C4—C7—N1	53.2 (3)	C10—C9—N1—C7	−160.10 (19)
C3—C4—C7—C8	112.2 (2)	C4—C7—N1—C9	71.1 (2)
C5—C4—C7—C8	−68.5 (3)	C8—C7—N1—C9	−165.5 (2)
N1—C9—C10—C11	116.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.82	2.05	2.794 (2)	150
N1—H1···O1ⁱⁱ	0.75 (2)	2.40 (2)	3.144 (3)	168 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆BrNO
M_r	306.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.1753 (10), 8.1939 (7), 14.0326 (11)
β (°)	93.333 (1)
V (Å³)	1397.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.93
Crystal size (mm)	0.20 × 0.16 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.592, 0.685
No. of measured, independent and observed [I > 2σ(I)] reflections	14961, 3094, 2119
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.077, 1.00
No. of reflections	3094
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.40

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.82	2.05	2.794 (2)	150.4
N1—H1···O1ⁱⁱ	0.75 (2)	2.40 (2)	3.144 (3)	168 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2.

Acknowledgements

This work was supported by the NASA Space Grant (grant No. nnx10am80h). The author thanks Professor R. G. Raptis for providing access to the X-ray diffractometer and also thanks Dr Indranil Chakraborty for his help with the structure refinement.

References

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