4-Bromo-3,5-dihydroxy­benzoic acid monohydrate

Kirsop, P.; Storey, J.M.D.; Harrison, W.T.A.

doi:10.1107/S1600536807003492

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages o1441-o1443

https://doi.org/10.1107/S1600536807003492

4-Bromo-3,5-dihydroxybenzoic acid monohydrate

Peter Kirsop,^a John M. D. Storey ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 19 January 2007; accepted 22 January 2007; online 23 February 2007)

The crystal packing of the title compound, C₇H₅BrO₄·H₂O, is influenced by O—H⋯O hydrogen bonds.

Comment

The title compound, (I) (Fig. 1), was prepared as part of our studies radical-mediated competitive cyclization reactions (Kirsop et al., 2007 ). Some crystal structures containing 4-bromo-3,5-dihydroxybenzoic acid and its deprotonated anion in combination with 4,4-bipyridine derivatives have been described recently by Varughese & Pedireddi (2006 ).

Compound (I) possesses normal geometric parameters (Allen et al., 1987 ). The dihedral angle between the mean plane of the C1–C6 benzne ring and the plane of the C7/O1/O2 grouping is 4.5 (5)°.

The crystal packing of (I) is influenced by O—H⋯O hydrogen bonds (Table 1). First, classical inversion dimers involving O4—H4⋯O3ⁱⁱⁱ and O4ⁱⁱⁱ—Hⁱⁱⁱ⋯O3 bonds of adjacent head-to-head carboxylic acid groups are formed (Fig. 2) [symmetry code: (iii) 1 − x, 1 − y, 1 − z]. Atom H4 appeared to be well ordered in a difference map, but the C7—O4 bond [1.288 (5) Å] is shorter and the C7=O3 bond [1.252 (5) Å] is longer than expected for a well ordered carboxylic acid group: the mean C—O and C=O bond lengths in carboxylic acid groups bound to an aromatic ring are 1.226 Å (σ = 0.020 Å) and 1.305 Å (σ = 0.020Å), respectively (Allen et al., 1987). This perhaps suggests partial disordering of H4 in (I), i.e. it is bound to both O3 and O4, but this was not visible in a difference map.

These dimeric pairs of 4-bromo-3,5-dihydroxybenzoic acid molecules are then linked into an infinite sheet by way of O1—H1⋯O4ⁱ bonds (Fig. 2). This results in distinctive R₆⁶(32) supramolecular loops (Bernstein et al., 1995 ). The O2–H2 hydroxyl group forms a hydrogen bond to a water molecule O atom. In turn, the water molecule acts as a donor for two more O—H⋯O interactions, to result in a three-dimensional network (Fig. 3).

Figure 1
A view of the molecular structure of (I)

, showing 50% probability displacement ellipsoids for the non-hydrogen atoms. The hydrogen bond is indicated by a double-dashed line.

Figure 2
Part of the crystal structure of (I)

, showing an R₆⁶(32) supramolecular loop arising from the connectivity of six organic molecules. Dashed lines indicate hydrogen bonds. [Symmetry codes as in Table 1

; additionally: (v) x, y, z − 1.]

Figure 3
Unit-cell contents for (I)

, with O—H⋯O hydrogen bonds indicated by double-dashed lines. [Symmetry codes as in Table 1

; additionally: (vi) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ + z; (vii) 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.]

Experimental

A commercial sample of 4-bromo-3,5-dihydroxybenzoic acid was recrystallized from water, to result in slightly translucent needles of (I).

Crystal data

C₇H₅BrO₄·H₂O
M_r = 251.04
Monoclinic, P 2₁ /c
a = 3.7065 (1) Å
b = 14.4963 (7) Å
c = 15.4548 (8) Å
β = 94.209 (3)°
V = 828.16 (6) Å³
Z = 4
D_x = 2.013 Mg m⁻³
Mo Kα radiation
μ = 4.95 mm⁻¹
T = 120 (2) K
Needle, colourless
0.12 × 0.02 × 0.01 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω and φ scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.588, T_max = 0.952
9660 measured reflections
1900 independent reflections
1466 reflections with I > 2σ(I)
R_int = 0.085
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.076
S = 1.08
1900 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + 1.4241P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.824 (19)	2.19 (3)	2.937 (4)	151 (4)
O2—H2⋯O5ⁱⁱ	0.835 (19)	1.82 (2)	2.641 (4)	169 (4)
O4—H4⋯O3ⁱⁱⁱ	0.834 (19)	1.79 (2)	2.620 (4)	175 (5)
O5—H6⋯O2^iv	0.828 (19)	2.18 (3)	2.918 (4)	149 (5)
O5—H7⋯O1	0.840 (19)	2.11 (2)	2.919 (4)	163 (4)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

O-bound H atoms were located in a difference map and their positions were refined with the distance restraint O—H = 0.85 (2) Å. U_iso(H) was set equal to 1.2U_eq(O). C-bound H atoms were placed in idealized positions, with C—H = 0.95 Å, and refined as riding, with U_iso(H) = 1.2U_eq(C).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807003492/lh2297sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807003492/lh2297Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

4-Bromo-3,5-dihydroxybenzoic acid monohydrate top

Crystal data top

C₇H₅BrO₄·H₂O	F(000) = 496
M_r = 251.04	D_x = 2.013 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1924 reflections
a = 3.7065 (1) Å	θ = 2.9–27.5°
b = 14.4963 (7) Å	µ = 4.95 mm⁻¹
c = 15.4548 (8) Å	T = 120 K
β = 94.209 (3)°	Needle, colourless
V = 828.16 (6) Å³	0.12 × 0.02 × 0.01 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	1900 independent reflections
Radiation source: fine-focus sealed tube	1466 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
ω and φ scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −4→4
T_min = 0.588, T_max = 0.952	k = −18→18
9660 measured reflections	l = −20→19

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)] = 0.049	Hydrogen site location: difmap and geom
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + 1.4241P] where P = (F_o² + 2F_c²)/3
1900 reflections	(Δ/σ)_max < 0.001
133 parameters	Δρ_max = 0.65 e Å⁻³
6 restraints	Δρ_min = −0.59 e Å⁻³

Special details top

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
C1	0.9836 (10)	0.1596 (3)	0.3025 (3)	0.0126 (9)
C2	0.8179 (9)	0.2346 (3)	0.2596 (3)	0.0130 (9)
C3	0.7138 (10)	0.3092 (3)	0.3078 (3)	0.0130 (9)
H3	0.5971	0.3604	0.2795	0.016*
C4	0.7790 (9)	0.3094 (3)	0.3969 (3)	0.0120 (9)
C5	0.9462 (10)	0.2347 (3)	0.4396 (3)	0.0138 (9)
H5	0.9906	0.2355	0.5010	0.017*
C6	1.0481 (10)	0.1587 (3)	0.3922 (3)	0.0136 (9)
C7	0.6600 (10)	0.3905 (3)	0.4454 (3)	0.0138 (9)
O1	0.7523 (8)	0.23889 (19)	0.1721 (2)	0.0193 (7)
H1	0.798 (11)	0.192 (2)	0.145 (3)	0.023*
O2	1.2073 (7)	0.08285 (19)	0.42874 (19)	0.0185 (7)
H2	1.261 (11)	0.092 (3)	0.4814 (14)	0.022*
O3	0.4904 (7)	0.45364 (18)	0.40498 (19)	0.0182 (7)
O4	0.7399 (8)	0.39319 (19)	0.5279 (2)	0.0208 (7)
H4	0.668 (11)	0.4435 (19)	0.546 (3)	0.025*
Br1	1.13095 (10)	0.05915 (3)	0.23622 (3)	0.01626 (13)
O5	0.4339 (8)	0.4063 (2)	0.0945 (2)	0.0259 (8)
H6	0.559 (10)	0.4521 (19)	0.108 (3)	0.031*
H7	0.561 (10)	0.360 (2)	0.110 (3)	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0125 (18)	0.009 (2)	0.016 (2)	0.0006 (15)	0.0028 (17)	−0.0048 (17)
C2	0.0119 (19)	0.0117 (19)	0.016 (2)	−0.0020 (15)	0.0017 (17)	−0.0004 (19)
C3	0.0139 (18)	0.010 (2)	0.016 (2)	−0.0010 (15)	0.0024 (17)	0.0059 (18)
C4	0.0131 (18)	0.009 (2)	0.014 (2)	−0.0002 (15)	0.0047 (17)	−0.0015 (17)
C5	0.0149 (19)	0.011 (2)	0.015 (3)	−0.0008 (16)	−0.0021 (17)	−0.0003 (18)
C6	0.0153 (19)	0.009 (2)	0.016 (2)	−0.0005 (15)	−0.0003 (17)	0.0036 (18)
C7	0.0142 (19)	0.011 (2)	0.016 (3)	−0.0023 (16)	0.0020 (17)	−0.0001 (18)
O1	0.0331 (16)	0.0136 (16)	0.0111 (18)	0.0046 (13)	0.0005 (13)	−0.0024 (13)
O2	0.0272 (15)	0.0150 (16)	0.0127 (17)	0.0028 (12)	−0.0032 (13)	−0.0031 (13)
O3	0.0242 (14)	0.0116 (16)	0.0184 (18)	0.0038 (12)	−0.0005 (13)	0.0024 (13)
O4	0.0350 (17)	0.0121 (16)	0.0154 (19)	0.0052 (13)	0.0027 (14)	−0.0045 (14)
Br1	0.0178 (2)	0.0136 (2)	0.0172 (2)	0.00327 (18)	−0.00002 (15)	−0.0047 (2)
O5	0.0401 (19)	0.0128 (16)	0.023 (2)	−0.0043 (13)	−0.0081 (16)	0.0011 (15)

Geometric parameters (Å, º) top

C1—C6	1.388 (6)	C5—H5	0.9500
C1—C2	1.393 (5)	C6—O2	1.352 (5)
C1—Br1	1.885 (4)	C7—O3	1.252 (5)
C2—O1	1.356 (5)	C7—O4	1.288 (5)
C2—C3	1.384 (5)	O1—H1	0.824 (19)
C3—C4	1.381 (6)	O2—H2	0.835 (19)
C3—H3	0.9500	O4—H4	0.834 (19)
C4—C5	1.390 (5)	O5—H6	0.828 (19)
C4—C7	1.479 (5)	O5—H7	0.840 (19)
C5—C6	1.391 (5)

C6—C1—C2	121.4 (4)	C4—C5—H5	120.2
C6—C1—Br1	120.0 (3)	C6—C5—H5	120.2
C2—C1—Br1	118.6 (3)	O2—C6—C1	117.6 (4)
O1—C2—C3	117.6 (4)	O2—C6—C5	123.4 (4)
O1—C2—C1	123.5 (4)	C1—C6—C5	119.0 (4)
C3—C2—C1	118.9 (4)	O3—C7—O4	122.9 (4)
C4—C3—C2	120.2 (4)	O3—C7—C4	119.1 (4)
C4—C3—H3	119.9	O4—C7—C4	118.0 (4)
C2—C3—H3	119.9	C2—O1—H1	116 (3)
C3—C4—C5	120.8 (4)	C6—O2—H2	110 (3)
C3—C4—C7	118.0 (4)	C7—O4—H4	108 (3)
C5—C4—C7	121.2 (4)	H6—O5—H7	106 (3)
C4—C5—C6	119.7 (4)

C6—C1—C2—O1	179.4 (3)	C2—C1—C6—O2	179.4 (3)
Br1—C1—C2—O1	0.8 (5)	Br1—C1—C6—O2	−2.0 (5)
C6—C1—C2—C3	−0.5 (5)	C2—C1—C6—C5	−0.3 (6)
Br1—C1—C2—C3	−179.1 (3)	Br1—C1—C6—C5	178.2 (3)
O1—C2—C3—C4	−179.0 (3)	C4—C5—C6—O2	−179.1 (3)
C1—C2—C3—C4	1.0 (5)	C4—C5—C6—C1	0.7 (5)
C2—C3—C4—C5	−0.6 (5)	C3—C4—C7—O3	3.4 (5)
C2—C3—C4—C7	−179.6 (3)	C5—C4—C7—O3	−175.5 (3)
C3—C4—C5—C6	−0.2 (5)	C3—C4—C7—O4	−175.9 (3)
C7—C4—C5—C6	178.7 (3)	C5—C4—C7—O4	5.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.82 (2)	2.19 (3)	2.937 (4)	151 (4)
O2—H2···O5ⁱⁱ	0.84 (2)	1.82 (2)	2.641 (4)	169 (4)
O4—H4···O3ⁱⁱⁱ	0.83 (2)	1.79 (2)	2.620 (4)	175 (5)
O5—H6···O2^iv	0.83 (2)	2.18 (3)	2.918 (4)	149 (5)
O5—H7···O1	0.84 (2)	2.11 (2)	2.919 (4)	163 (4)

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

Acknowledgements

The authors thank the EPSRC's UK National Crystallography Service, University of Southampton, for the data collection.

References

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