Crystal structure of 4-amino-2,6-di­chloro­phenol

McDonald, K.J.; Desikan, V.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2056989015009172

organic compounds

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Crystal structure of 4-amino-2,6-dichlorophenol

Kyle J. McDonald,^a Vasumathi Desikan,^a James A. Golen ^b and David R. Manke ^b ^*

^aDepartment of Science & Math, Massasoit Community College, 1 Massasoit Boulevard, Brockton, MA 02302, USA, and ^bDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by K. Fejfarova, Institute of Macromolecular Chemistry, AS CR, v.v.i, Czech Republic (Received 5 May 2015; accepted 13 May 2015; online 20 May 2015)

The title compound, C₆H₅Cl₂NO, has a single planar molecule in the asymmetric unit with the non-H atoms possessing a mean deviation from planarity of 0.020 Å. In the crystal, O—H⋯N hydrogen bonds lead to the formation of infinite chains along [101] which are further linked by N—H⋯O hydrogen bonds, forming (010) sheets.

Keywords: crystal structure; aminophenols; hydrogen bonding.

CCDC reference: 1400729

1. Related literature

For the crystal structure of the parent p-aminophenol, see: Brown (1951 ). For other related structures, see: Ermer & Eling (1994 ); Dey et al. (2005 ); Bacchi et al. (2009 ).

2. Experimental

2.1. Crystal data

C₆H₅Cl₂NO
M_r = 178.02
Monoclinic, P 2₁ /n
a = 4.6064 (5) Å
b = 11.7569 (12) Å
c = 13.2291 (13) Å
β = 96.760 (5)°
V = 711.47 (13) Å³
Z = 4
Cu Kα radiation
μ = 7.59 mm⁻¹
T = 120 K
0.4 × 0.2 × 0.1 mm

2.2. Data collection

Bruker D8 Venture CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ) T_min = 0.425, T_max = 0.754
7481 measured reflections
1402 independent reflections
1273 reflections with I ≥ 2σ(I)
R_int = 0.043

2.3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.091
S = 1.05
1402 reflections
99 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.85 (2)	1.82 (2)	2.653 (2)	168 (2)
N1—H1a⋯O1ⁱⁱ	0.87 (1)	2.05 (1)	2.921 (2)	177 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ) and OLEX2.refine (Bourhis et al., 2015 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2 and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1400729

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015009172/ff2137sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009172/ff2137Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015009172/ff2137Isup3.cml

checkCIF report

Comment top

The hydrogen bonding networks of aminophenols have been explored as hydroxy and amino groups are complementary hydrogen bonding donors and acceptors. This is exemplified in p-aminophenol, which exhibits a supertetrahedral hydrogen bonded architecture where all hydrogen bonding donors and acceptors are saturated (Brown, 1951; Ermer et al., 1994). The mono-substitution in 4-amino-2-methylphenol and 4-amino-3-methylphenol yields a square motif structure that again exhibits saturation among hydrogen bonding donors and acceptors (Dey et al., 2005). The more sterically encumbered substitution of 4-amino-2,6-diphenylphenol prevents the saturation in hydrogen bonding, with only O–H···N and N–H···aryl interactions observed (Bacchi et al., 2009). The 2,6-dichloro substitution of the title compound also prevents saturation in its hydrogen bonding network.

The molecular structure of the title compound demonstrates a planar molecule with a mean deviation from the plane of the non-hydrogen atoms of 0.020 Å. Intermolecular hydrogen bonding between O1–H1···N1 results in infinite chains along [101] which combine with intermolecular hydrogen bonding between N1–H1a···O1 to give (010) sheets. The packing for the title compound indicating hydrogen bonding is shown in Figure 2.

Experimental top

A commercial sample (Aldrich) was used for the crystallization. Crystals suitable for single crystal X-ray analysis were grown by slow evaporation of a methanol solution.

Refinement top

All non-hydrogen atoms were refined anisotropically (Olex2) by full matrix least squares on F². Hydrogen atoms H1, H1a and H1b were found from a Fourier difference map. H1 was allowed to refine freely with an isotropic displacement parameter of 1.20 times U_eq of the parent O atom. H1a and H1b were refined with a fixed distance of 0.87 (0.005) Å and isotropic displacement parameters of 1.20 times U_eq of the parent N atom. The two remaining hydrogen atoms were placed in calculated positions and then refined with riding model with C–H lengths of 0.95 Å with isotropic displacement parameters set to 1.20 times U_eq of the parent C atom.

Related literature top

For the crystal structure of the parent p-aminophenol, see: Brown (1951). For other related structures, see: Ermer & Eling (1994); Dey et al. (2005); Bacchi et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) and olex2.refine (Bourhis et al., 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

4-Amino-2,6-dichlorophenol top

Crystal data top

C₆H₅Cl₂NO	F(000) = 363.7579
M_r = 178.02	D_x = 1.662 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 5198 reflections
a = 4.6064 (5) Å	θ = 5.1–72.2°
b = 11.7569 (12) Å	µ = 7.59 mm⁻¹
c = 13.2291 (13) Å	T = 120 K
β = 96.760 (5)°	Plate, colourless
V = 711.47 (13) Å³	0.4 × 0.2 × 0.1 mm
Z = 4

Data collection top

Bruker D8 Venture CMOS diffractometer	1402 independent reflections
Radiation source: microfocus Cu	1273 reflections with I ≥ 2σ(I)
HELIOS MX monochromator	R_int = 0.043
Detector resolution: 102.4 pixels mm^-1	θ_max = 72.2°, θ_min = 5.1°
ϕ and ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −14→14
T_min = 0.425, T_max = 0.754	l = −12→16
7481 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	7 constraints
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0618P)² + 0.1912P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1402 reflections	Δρ_max = 0.33 e Å⁻³
99 parameters	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₆H₅Cl₂NO	V = 711.47 (13) Å³
M_r = 178.02	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 4.6064 (5) Å	µ = 7.59 mm⁻¹
b = 11.7569 (12) Å	T = 120 K
c = 13.2291 (13) Å	0.4 × 0.2 × 0.1 mm
β = 96.760 (5)°

Data collection top

Bruker D8 Venture CMOS diffractometer	1402 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	1273 reflections with I ≥ 2σ(I)
T_min = 0.425, T_max = 0.754	R_int = 0.043
7481 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	2 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.33 e Å⁻³
1402 reflections	Δρ_min = −0.35 e Å⁻³
99 parameters

Special details top

Experimental. Absorption correction: SADABS-2014/4 (Bruker, 2014) was used for absorption correction. wR2(int) was 0.1370 before and 0.0641 after correction. The Ratio of minimum to maximum transmission is 0.5642. The λ/2 correction factor is 0.00150.

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

	x	y	z	U_iso*/U_eq
Cl1	0.10618 (10)	0.09750 (4)	0.70434 (3)	0.02213 (17)
Cl2	0.79187 (11)	0.44532 (4)	0.61176 (4)	0.02666 (18)
O1	0.4519 (3)	0.30303 (12)	0.74687 (10)	0.0214 (3)
N1	0.4522 (4)	0.13356 (14)	0.35171 (12)	0.0199 (4)
C1	0.4563 (4)	0.26523 (16)	0.65055 (14)	0.0176 (4)
C4	0.4607 (4)	0.17796 (16)	0.45234 (13)	0.0176 (4)
C5	0.6112 (4)	0.27756 (16)	0.48060 (14)	0.0196 (4)
H5	0.7170 (4)	0.31620 (16)	0.43359 (14)	0.0235 (5)*
C2	0.3011 (4)	0.16753 (16)	0.61822 (14)	0.0171 (4)
C3	0.3014 (4)	0.12337 (16)	0.52110 (14)	0.0182 (4)
H3	0.1938 (4)	0.05638 (16)	0.50165 (14)	0.0219 (5)*
C6	0.6052 (4)	0.31990 (16)	0.57788 (14)	0.0179 (4)
H1	0.615 (5)	0.329 (2)	0.7732 (18)	0.0215 (5)*
H1a	0.601 (3)	0.1551 (19)	0.3217 (15)	0.0215 (5)*
H1b	0.451 (5)	0.0598 (4)	0.3523 (17)	0.0215 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0232 (3)	0.0246 (3)	0.0204 (3)	−0.00409 (16)	0.00988 (19)	0.00083 (17)
Cl2	0.0334 (3)	0.0245 (3)	0.0225 (3)	−0.01014 (19)	0.0052 (2)	−0.00026 (18)
O1	0.0193 (6)	0.0298 (7)	0.0156 (7)	−0.0039 (6)	0.0046 (5)	−0.0042 (6)
N1	0.0206 (8)	0.0247 (9)	0.0151 (8)	0.0013 (6)	0.0057 (6)	−0.0009 (6)
C1	0.0146 (8)	0.0225 (9)	0.0159 (9)	0.0027 (7)	0.0023 (7)	0.0008 (7)
C4	0.0138 (8)	0.0248 (9)	0.0142 (9)	0.0050 (7)	0.0009 (7)	0.0005 (7)
C5	0.0177 (9)	0.0244 (10)	0.0173 (9)	0.0005 (7)	0.0048 (7)	0.0054 (7)
C2	0.0144 (8)	0.0215 (9)	0.0163 (9)	0.0011 (7)	0.0051 (7)	0.0035 (7)
C3	0.0148 (8)	0.0217 (9)	0.0185 (10)	0.0005 (7)	0.0029 (7)	−0.0007 (7)
C6	0.0158 (8)	0.0188 (9)	0.0194 (9)	−0.0007 (7)	0.0026 (7)	0.0016 (7)

Geometric parameters (Å, º) top

Cl1—C2	1.7387 (18)	C1—C6	1.401 (3)
Cl2—C6	1.7389 (19)	C4—C5	1.389 (3)
O1—C1	1.352 (2)	C4—C3	1.391 (3)
O1—H1	0.85 (2)	C5—H5	0.9500
N1—C4	1.426 (2)	C5—C6	1.383 (3)
N1—H1a	0.870 (5)	C2—C3	1.386 (3)
N1—H1b	0.867 (5)	C3—H3	0.9500
C1—C2	1.393 (3)

H1—O1—C1	113.3 (16)	C6—C5—C4	119.33 (17)
H1a—N1—C4	112.6 (15)	C6—C5—H5	120.34 (11)
H1b—N1—C4	110.9 (15)	C1—C2—Cl1	118.37 (14)
H1b—N1—H1a	108 (2)	C3—C2—Cl1	119.15 (14)
C2—C1—O1	119.75 (16)	C3—C2—C1	122.47 (16)
C6—C1—O1	123.97 (17)	C2—C3—C4	119.44 (18)
C6—C1—C2	116.26 (17)	H3—C3—C4	120.28 (11)
C5—C4—N1	121.18 (17)	H3—C3—C2	120.28 (11)
C3—C4—N1	118.87 (18)	C1—C6—Cl2	118.64 (14)
C3—C4—C5	119.85 (17)	C5—C6—Cl2	118.79 (14)
H5—C5—C4	120.34 (10)	C5—C6—C1	122.57 (17)

Cl1—C2—C3—C4	−178.98 (14)	C4—C5—C6—Cl2	−179.43 (14)
O1—C1—C2—Cl1	−0.1 (2)	C4—C5—C6—C1	1.0 (3)
O1—C1—C2—C3	−178.74 (17)	C5—C4—C3—C2	−1.7 (3)
O1—C1—C6—Cl2	−1.1 (3)	C2—C1—C6—Cl2	177.57 (13)
O1—C1—C6—C5	178.43 (17)	C2—C1—C6—C5	−2.9 (3)
N1—C4—C5—C6	177.70 (17)	C3—C4—C5—C6	1.3 (3)
N1—C4—C3—C2	−178.14 (17)	C6—C1—C2—Cl1	−178.80 (13)
C1—C2—C3—C4	−0.3 (3)	C6—C1—C2—C3	2.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.85 (2)	1.82 (2)	2.653 (2)	168 (2)
N1—H1a···O1ⁱⁱ	0.87 (1)	2.05 (1)	2.921 (2)	177 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.85 (2)	1.82 (2)	2.653 (2)	168 (2)
N1—H1a···O1ⁱⁱ	0.870 (5)	2.052 (6)	2.921 (2)	177 (2)

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

Acknowledgements

We greatly acknowledge support from the National Science Foundation (CHE-1429086).

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 6| June 2015| Page o406

doi:10.1107/S2056989015009172

Open

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