3-Amino­phenyl­boronic acid monohydrate

Araceli Vega; Maria Zarate; Hugo Tlahuext; Herbert Höpfl

doi:10.1107/S1600536810015655

. 2010 May 8;66(Pt 6):o1260. doi: 10.1107/S1600536810015655

3-Aminophenylboronic acid monohydrate

Araceli Vega ^a, Maria Zarate ^a, Hugo Tlahuext ^a, Herbert Höpfl ^a,^*

PMCID: PMC2979464 PMID: 21579363

Abstract

In the title compound, C₆H₈BNO₂·H₂O, the almost planar boronic acid molecules (r.m.s. deviation = 0.044 Å) form inversion dimers, linked by pairs of O—H⋯O hydrogen bonds. The water molecules link these dimers into [100] chains by way of O—H⋯O hydrogen bonds, and N—H⋯O links generate (100) sheets.

Related literature

For background to the synthesis, structures and applications of phenylboronic acid derivatives, see: Barba & Betanzos (2007 ▶); Barba et al. (2004 ▶, 2006 ▶); Bernstein et al. (1995 ▶); Christinat et al. (2008 ▶); Dreos et al. (2002 ▶); Fujita et al. (2008 ▶); Höpfl (2002 ▶); Hall (2005 ▶); Lulinski et al. (2007 ▶); Miyaura & Suzuki (1995 ▶); Severin (2009 ▶); Shinkai et al. (2001 ▶); Smith et al. (2008 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

C₆H₈BNO₂·H₂O
M _r = 154.96
Monoclinic,
a = 7.1211 (8) Å
b = 13.8548 (15) Å
c = 7.8475 (8) Å
β = 100.663 (2)°
V = 760.88 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.44 × 0.38 × 0.34 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.89, T _max = 1.00
7077 measured reflections
1341 independent reflections
1258 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.088
S = 1.03
1341 reflections
124 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus-NT (Bruker, 2001 ▶); data reduction: SAINT-Plus-NT; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810015655/hb5409sup1.cif

e-66-o1260-sup1.cif^{(15KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015655/hb5409Isup2.hkl

e-66-o1260-Isup2.hkl^{(66.2KB, 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
O1—H1′⋯O2ⁱ	0.84 (1)	1.92 (1)	2.7583 (13)	174 (2)
N1—H1A⋯O31ⁱⁱ	0.86 (1)	2.21 (1)	3.0661 (15)	177 (1)
N1—H1B⋯O1ⁱⁱⁱ	0.86 (1)	2.43 (1)	3.1854 (15)	147 (1)
O2—H2′⋯O31	0.84 (1)	1.91 (1)	2.7159 (13)	161 (2)
O31—H31A⋯N1^iv	0.84 (1)	2.07 (1)	2.9040 (15)	173 (2)
O31—H31B⋯O1^v	0.84 (1)	2.05 (1)	2.8810 (13)	170 (2)

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

Acknowledgments

This work was supported by the Consejo Nacional de Ciencia y Tecnología (CIAM-59213).

supplementary crystallographic information

Comment

Substituted phenylboronic acid derivatives have been prepared mainly for applications in organic synthesis (Miyaura & Suzuki, 1995; Hall, 2005) and for molecular recognition of biochemically active molecules (Shinkai et al., 2001). More recently, such boronic acid derivatives have attracted attention also as building blocks for the self-assembly of macrocyclic and polymeric assemblies. For this purpose, the boronic acid is generally converted to an ester (boronate) via condensation with an aliphatic or aromatic diol, which is then assembled to a macromolecular structure via reaction of the additional functional group attached to the B-phenyl ring (Höpfl, 2002; Fujita et al., 2008; Severin, 2009). In this context, 3-aminophenylboronic acid has been employed for the generation of macrocycles and cages (Dreos et al., 2002; Barba et al., 2004 and 2006; Barba & Betanzos, 2007; Christinat et al., 2008).

We report herein on the molecular and crystal structure of 3-aminophenylboronic acid monohydrate (I).

The asymmetric unit of I contains one 3-aminophenylboronic acid and one water molecule (Figure 1). The boronic acid molecules are associated through the well-known -B(OH)₂···(HO)₂B-synthon (motif A) with the graph set R₂²(8) (Bernstein et al., 1995), in which each B(OH)₂ group has syn-anti conformation (with respect to the H atoms), thus allowing for the formation of additional hydrogen bonds with the water molecules included in the crystal lattice. These (B)O—H···O_w hydrogen bonds give rise to a cyclic water-expanded motif B [graph set R₆⁶(12)] of the boronic acid homodimer, thus generating a 1D chain along axis a (Figure 2). The (OH)₆ ring has chair-conformation and has been observed previously in the crystal structures of 3,5-dibromo-2-formylphenylboronic acid monohydrate (Lulinski et al., 2007), 5-quinolineboronic acid monohydrate (Zhang et al., 2007) and 2,6-dichloro-3-pyridylboronic acid hemihydrate (Smith et al., 2008). The 1D chains are interconnected through O_w—H···N, N—H···O_w and N—H···O(B) hydrogen bonds to give an overall 3D hydrogen bonded network (Table 1).

Experimental

3-Aminophenylboronic acid monohydrate is a commercially available product that has been crystallized from a solvent mixture of benzene, methanol and water to generate colourless blocks of (I); M.p. 368 K.