(4-Hydr­oxy-3-nitro­benz­yl)methyl­ammonium chloride

Grant A Boyle; Hendrik G Kruger; Glenn E M Maguire; Jason Paraskevopoulos

doi:10.1107/S160053680800473X

. 2008 Feb 27;64(Pt 3):o625. doi: 10.1107/S160053680800473X

(4-Hydroxy-3-nitrobenzyl)methylammonium chloride

Grant A Boyle ^a, Hendrik G Kruger ^a, Glenn E M Maguire ^a,^*, Jason Paraskevopoulos ^a

PMCID: PMC2960751 PMID: 21201957

Abstract

The title compound, C₈H₁₁N₂O₃ ⁺·Cl⁻, was synthesized as an intermediate in the development of a new sugar sensor. The structure displays N—H⋯Cl and O—H⋯O hydrogen bonding, as well as weak O—H⋯Cl interactions and π–π stacking (3.298 Å). There are two formula units in the asymmetric unit.

Related literature

For related literature, see: James et al. (1995 ▶).

Experimental

Crystal data

C₈H₁₁N₂O₃ ⁺·Cl⁻
M _r = 218.64
Triclinic,
a = 7.7650 (2) Å
b = 10.5922 (3) Å
c = 13.5987 (4) Å
α = 70.262 (1)°
β = 78.368 (1)°
γ = 76.459 (1)°
V = 1014.27 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 173 (2) K
0.48 × 0.39 × 0.36 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: none
11798 measured reflections
4901 independent reflections
4057 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.094
S = 1.06
4901 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: Mercury (Macrae et al., 2006 ▶) and WinGX (Farrugia, 1999 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800473X/hg2362sup1.cif

e-64-0o625-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800473X/hg2362Isup2.hkl

e-64-0o625-Isup2.hkl^{(235.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2A⋯Cl1A	0.92	2.23	3.1301 (11)	167
N2A—H2B⋯Cl1B	0.92	2.18	3.0898 (11)	173
O1A—H1A⋯O2A	0.84	1.89	2.5917 (14)	140
O1A—H1A⋯Cl1Bⁱ	0.84	2.87	3.3918 (10)	122
N2B—H2C⋯Cl1Aⁱⁱ	0.92	2.17	3.0775 (11)	168
N2B—H2D⋯Cl1Bⁱⁱⁱ	0.92	2.26	3.1671 (10)	168
O1B—H1B⋯O2B	0.84	1.88	2.5860 (14)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We thank Dr Manuel Fernandes of the Jan Boeyens Structural Chemistry Laboratory at the University of the Witwatersrand for his assistance in the acquisition of the crystallographic data. Aspen Pharmacare is acknowledged for their financial support.

supplementary crystallographic information

Comment

The title compound, (I), was synthesized as an intermediate in the development of a new sugar sensor (James et al., 1995). The compound itself is also novel and is being reported for the first time.

The structure consists of two molecules in the asymmetric unit (Figure 1). The cation consists of a planar nitro phenol ring with a methylaminomethyl group in the para position with respect to the hydroxy group (O1) on the ring. The methylammonium groups attached to the methylene carbon (C7) deviate from the plane of the ring with a torsion angle of -121.52 (13)° for C3A—C4A—C7A—N2A and -46.81 (16)° for C3B—C4B—C7B—N2B.

The structure exhibits both intermolecular (N1—H1···Cl) and intramolecular (O1—H1···O2) hydrogen bonding interactions (Table 1, Figure 2). The chloride ions act as hydrogen bond acceptors between adjacent molecules. Weak interactions are also observed between O1—H1···Cl1. These interactions, with a bond length of 2.87Å (O1A—H1A···Cl1Bⁱ), are more likely weak Van der Waals interactions rather than true hydrogen bonds. See Table 1 for a full list of all hydrogen bond interactions. An interdigitated, layered structure is observed with the aromatic groups π–π stacking above each other and the methylaminomethyl group interacting with the chloride ions in hydrogen bonded layers (Figure 3).

Experimental

4-Chloromethyl-2-nitrophenol, 3.8 g (20 mmol), was dissolved in DMF (30 ml). To this was added triethylamine (3 ml) followed by 40% methylamine in H₂O (5 ml, 58 mmol). The reaction was heated to 333 K and left to stir overnight. The solvent was removed under vacuum to afford an orange solid, which was recrystallized from methanol at room temperature. Yield 3.49 g (80%). Decomposition point 373–375 K.

¹H-NMR (400 MHz, D₂O): p.p.m. = 0.00 (TMS), 2.62 (s, 3H, CH₃), 4.12 (s, 2H, CH₂), 7.14 (d, J = 8.5 Hz, 1H, H5), 7.60 (d, J = 8.5 Hz, 1H, H6), 8.13 (s, 1H, H3).¹³C-NMR(100 MHz, D₂O): p.p.m. = 0.00 (TMS), 32.58 (CH₃), 51.50 (CH₂),121.30 (C6), 123.50 (C4), 127.75 (C3), 136.86 (C2), 139.04 (C5), 154.76 (C1).