2,3,4-Trihydroxy­benzaldehyde

Ng, S.W.

doi:10.1107/S1600536808022241

organic compounds

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Volume 64| Part 8| August 2008| Page o1565

doi:10.1107/S1600536808022241

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2,3,4-Trihydroxybenzaldehyde

Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 15 July 2008; accepted 15 July 2008; online 23 July 2008)

The title compound, C₇H₆O₄, crystallizes with two independent molecules in the asymmetric unit. In both molecules, the 2-hydroxy group is bound via intramolecular hydrogen bonds to the aldehyde group. The molecules interact through O—H⋯O hydrogen bonds to form a three-dimensional network structure; each hydroxy group serves as a donor to only one acceptor atom.

Related literature

For some references on hydroxy-substituted benzaldehydes, see: Kretz et al. (2007 ); Ng (2005 ). For the crystal structures of Schiff base derivatives of 2,3,4-trihydroxysalicylaldehyde, see: Petek et al. (2006 ); Sun et al. (2007 ).

Experimental

Crystal data

C₇H₆O₄
M_r = 154.12
Monoclinic, C c
a = 3.6222 (3) Å
b = 24.006 (2) Å
c = 14.8965 (9) Å
β = 93.524 (5)°
V = 1292.9 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 (2) K
0.30 × 0.03 × 0.03 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
5464 measured reflections
1491 independent reflections
1087 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.132
S = 1.01
1491 reflections
217 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.84 (1)	1.99 (5)	2.631 (5)	133 (6)
O3—H3⋯O7ⁱ	0.84 (1)	2.04 (3)	2.816 (5)	153 (6)
O4—H4⋯O1ⁱⁱ	0.84 (1)	1.90 (3)	2.701 (5)	159 (6)
O6—H6⋯O5	0.84 (1)	1.87 (3)	2.653 (5)	154 (6)
O7—H7⋯O2	0.84 (1)	2.02 (3)	2.772 (5)	149 (6)
O8—H8⋯O5ⁱⁱⁱ	0.84 (1)	1.86 (2)	2.679 (5)	162 (7)
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022241/bt2748sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022241/bt2748Isup2.hkl

checkCIF report

Comment top

2,3,4-Trihydroxybenzaldehyde condenses with primary amines to afford Schiff bases. The crystal structures of only few such Schiff bases have been reported. The 2-fluoroaniline derivative exists as a zwitterion as the hydrogen atom of the 2-hydroxy substituent is transferred to the imino nitrogen atom (Petek et al., 2006). On the other hand, the antipyrine derivative has the expected neutral structure (Sun et al., 2007). Although there are several structural studies on hydroxy-substituted benzaldehydes (Kretz et al., 2007; Ng, 2005), the structure of 2,3,4-trihydroxybenzaldehyde has not been reported.

2,3,4-Trihydroxybenzaldehyde (Scheme I) crystallizes with two independent molecules in the asymmetric unit. In both, the 2-hydroxy group is hydrogen-bonded to the aldehyde group via an intramolecular hydrogen bond (Fig. 1). The molecules interact through O–H···O hydrogen bonds to form a three-dimensional network structure; each hydroxy group serves as donor to only one acceptor atom.

Related literature top

For some references on hydroxy-substituted benzaldehydes, see: Kretz et al. (2007); Ng (2005). For the crystal structures of the Schiff base derivatives of 2,3,4-trihydroxysalicylaldehyde, see: Petek et al. (2006); Sun et al. (2007).

Experimental top

Commercially available 2,3,4-trihydroxybenzaldehyde was recrystallized from ethanol to furnished light-brown, needled-shaped crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Plot (Barbour, 2001) of the two independent molecules of 2,3,4-trihydroxybenzaldehyde with 50% probability ellipsoids. Hydrogen atoms are drawn as spheres of arbitrary radius.

2,3,4-Trihydroxybenzaldehyde top

Crystal data top

C₇H₆O₄	F(000) = 640
M_r = 154.12	D_x = 1.584 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C c	Cell parameters from 446 reflections
a = 3.6222 (3) Å	θ = 2.8–19.5°
b = 24.006 (2) Å	µ = 0.13 mm⁻¹
c = 14.8965 (9) Å	T = 100 K
β = 93.524 (5)°	Needle, light brown
V = 1292.9 (2) Å³	0.30 × 0.03 × 0.03 mm
Z = 8

Data collection top

Bruker SMART APEX diffractometer	1087 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.088
Graphite monochromator	θ_max = 27.5°, θ_min = 1.7°
ω scans	h = −4→3
5464 measured reflections	k = −30→30
1491 independent reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.132	w = 1/[σ²(F_o²) + (0.0467P)² + 2.3366P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
1491 reflections	Δρ_max = 0.30 e Å⁻³
217 parameters	Δρ_min = −0.32 e Å⁻³
8 restraints	Absolute structure: Friedel pairs were merged
Primary atom site location: structure-invariant direct methods

Crystal data top

C₇H₆O₄	V = 1292.9 (2) Å³
M_r = 154.12	Z = 8
Monoclinic, Cc	Mo Kα radiation
a = 3.6222 (3) Å	µ = 0.13 mm⁻¹
b = 24.006 (2) Å	T = 100 K
c = 14.8965 (9) Å	0.30 × 0.03 × 0.03 mm
β = 93.524 (5)°

Data collection top

Bruker SMART APEX diffractometer	1087 reflections with I > 2σ(I)
5464 measured reflections	R_int = 0.088
1491 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	8 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.30 e Å⁻³
1491 reflections	Δρ_min = −0.32 e Å⁻³
217 parameters	Absolute structure: Friedel pairs were merged

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

	x	y	z	U_iso*/U_eq
O1	0.5000 (11)	0.19999 (15)	0.5000 (3)	0.0203 (9)
O2	0.4561 (11)	0.18738 (14)	0.6744 (3)	0.0177 (9)
H2	0.432 (19)	0.172 (2)	0.6236 (19)	0.027*
O3	0.2999 (11)	0.23611 (14)	0.8356 (2)	0.0186 (9)
H3	0.253 (18)	0.2022 (8)	0.827 (4)	0.028*
O4	0.0704 (11)	0.34509 (15)	0.8358 (3)	0.0187 (9)
H4	0.046 (19)	0.324 (2)	0.879 (3)	0.028*
O5	1.4505 (11)	−0.00937 (16)	1.0289 (3)	0.0206 (9)
O6	1.1992 (11)	0.08512 (14)	0.9559 (2)	0.0195 (9)
H6	1.297 (17)	0.062 (2)	0.993 (3)	0.029*
O7	0.8968 (11)	0.13655 (14)	0.8094 (3)	0.0187 (9)
H7	0.801 (18)	0.142 (2)	0.7575 (19)	0.028*
O8	0.7396 (10)	0.07867 (14)	0.6555 (2)	0.0172 (9)
H8	0.696 (19)	0.056 (2)	0.613 (3)	0.026*
C1	0.3888 (16)	0.2489 (2)	0.5099 (4)	0.0182 (12)
H1	0.3571	0.2717	0.4579	0.022*
C2	0.3068 (15)	0.2725 (2)	0.5942 (4)	0.0140 (11)
C3	0.3431 (15)	0.2416 (2)	0.6752 (4)	0.0148 (11)
C4	0.2636 (16)	0.2646 (2)	0.7557 (4)	0.0151 (12)
C5	0.1496 (15)	0.3204 (2)	0.7578 (4)	0.0153 (11)
C6	0.1124 (15)	0.3520 (2)	0.6789 (4)	0.0171 (12)
H6A	0.0328	0.3896	0.6812	0.021*
C7	0.1914 (16)	0.3285 (2)	0.5982 (4)	0.0184 (12)
H7A	0.1680	0.3501	0.5448	0.022*
C8	1.3595 (16)	−0.0319 (2)	0.9554 (4)	0.0182 (12)
H8A	1.4039	−0.0707	0.9498	0.022*
C9	1.1938 (15)	−0.0035 (2)	0.8791 (4)	0.0146 (11)
C10	1.1232 (16)	0.0546 (2)	0.8814 (4)	0.0150 (11)
C11	0.9686 (16)	0.08085 (19)	0.8055 (4)	0.0142 (11)
C12	0.8902 (15)	0.0499 (2)	0.7274 (3)	0.0142 (11)
C13	0.9584 (15)	−0.0072 (2)	0.7239 (4)	0.0160 (12)
H13	0.9043	−0.0276	0.6701	0.019*
C14	1.1054 (15)	−0.0333 (2)	0.7999 (4)	0.0167 (12)
H14	1.1480	−0.0723	0.7988	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.023 (2)	0.0189 (19)	0.019 (2)	0.0023 (16)	0.0050 (18)	−0.0053 (15)
O2	0.025 (2)	0.0122 (17)	0.015 (2)	0.0033 (16)	−0.0038 (18)	−0.0012 (15)
O3	0.032 (3)	0.0111 (17)	0.013 (2)	0.0021 (16)	0.0006 (18)	0.0028 (14)
O4	0.027 (2)	0.0147 (17)	0.015 (2)	0.0041 (17)	0.0023 (17)	−0.0010 (15)
O5	0.023 (2)	0.023 (2)	0.015 (2)	0.0024 (17)	−0.0034 (17)	0.0012 (16)
O6	0.032 (3)	0.0147 (18)	0.011 (2)	−0.0003 (16)	−0.0070 (18)	−0.0039 (15)
O7	0.029 (3)	0.0124 (16)	0.0140 (18)	0.0040 (16)	−0.0032 (17)	−0.0030 (15)
O8	0.023 (2)	0.0163 (18)	0.011 (2)	0.0023 (16)	−0.0065 (17)	−0.0020 (14)
C1	0.017 (3)	0.020 (3)	0.017 (3)	0.001 (2)	−0.005 (3)	0.003 (2)
C2	0.010 (3)	0.018 (2)	0.014 (3)	0.001 (2)	0.000 (2)	−0.003 (2)
C3	0.007 (3)	0.015 (2)	0.022 (3)	0.002 (2)	−0.002 (2)	−0.002 (2)
C4	0.016 (3)	0.014 (2)	0.015 (3)	0.001 (2)	−0.002 (2)	0.001 (2)
C5	0.011 (3)	0.017 (3)	0.019 (3)	−0.001 (2)	0.003 (2)	−0.001 (2)
C6	0.014 (3)	0.012 (2)	0.025 (3)	0.002 (2)	0.000 (3)	0.000 (2)
C7	0.021 (3)	0.017 (3)	0.017 (3)	0.002 (2)	−0.001 (3)	0.003 (2)
C8	0.014 (3)	0.019 (3)	0.022 (3)	0.000 (2)	0.002 (2)	0.006 (2)
C9	0.012 (3)	0.015 (2)	0.016 (3)	0.000 (2)	0.001 (2)	0.001 (2)
C10	0.011 (3)	0.021 (3)	0.014 (3)	−0.002 (2)	0.000 (2)	−0.004 (2)
C11	0.013 (3)	0.012 (2)	0.017 (3)	0.000 (2)	0.001 (2)	−0.005 (2)
C12	0.009 (3)	0.020 (2)	0.014 (3)	0.000 (2)	0.000 (2)	0.003 (2)
C13	0.013 (3)	0.020 (3)	0.014 (3)	0.000 (2)	−0.002 (2)	−0.004 (2)
C14	0.012 (3)	0.014 (3)	0.024 (3)	0.001 (2)	−0.001 (2)	0.000 (2)

Geometric parameters (Å, º) top

O1—C1	1.253 (6)	C9—C10	1.421 (7)
O2—C3	1.365 (6)	C10—C11	1.382 (8)
O3—C4	1.372 (6)	C11—C12	1.395 (7)
O4—C5	1.351 (6)	C12—C13	1.394 (7)
O5—C8	1.248 (7)	C13—C14	1.372 (7)
O6—C10	1.343 (6)	O2—H2	0.84 (1)
O7—C11	1.364 (6)	O3—H3	0.84 (1)
O8—C12	1.361 (6)	O4—H4	0.84 (1)
C1—C2	1.426 (7)	O6—H6	0.84 (1)
C2—C7	1.409 (7)	O7—H7	0.84 (1)
C2—C3	1.416 (7)	O8—H8	0.84 (1)
C3—C4	1.367 (7)	C1—H1	0.9500
C4—C5	1.402 (7)	C6—H6A	0.9500
C5—C6	1.398 (7)	C7—H7A	0.9500
C6—C7	1.374 (7)	C8—H8A	0.9500
C8—C9	1.425 (8)	C13—H13	0.9500
C9—C14	1.398 (7)	C14—H14	0.9500

C3—O2—H2	114 (4)	C10—C9—C8	121.1 (5)
C4—O3—H3	110 (5)	O6—C10—C11	118.6 (4)
C5—O4—H4	116 (5)	O6—C10—C9	121.9 (5)
C10—O6—H6	104 (4)	C11—C10—C9	119.5 (5)
C11—O7—H7	101 (4)	O7—C11—C10	118.7 (5)
C12—O8—H8	108 (4)	O7—C11—C12	121.9 (5)
O1—C1—C2	124.2 (5)	C10—C11—C12	119.4 (4)
C7—C2—C3	118.4 (5)	O8—C12—C13	122.3 (5)
C7—C2—C1	119.7 (5)	O8—C12—C11	115.9 (4)
C3—C2—C1	121.9 (4)	C13—C12—C11	121.9 (5)
O2—C3—C4	118.2 (5)	C14—C13—C12	118.6 (5)
O2—C3—C2	120.4 (5)	C13—C14—C9	121.3 (5)
C4—C3—C2	121.5 (4)	O1—C1—H1	117.9
C3—C4—O3	123.1 (4)	C2—C1—H1	117.9
C3—C4—C5	118.9 (5)	C7—C6—H6A	120.1
O3—C4—C5	118.0 (5)	C5—C6—H6A	120.1
O4—C5—C6	118.0 (5)	C6—C7—H7A	119.8
O4—C5—C4	121.1 (5)	C2—C7—H7A	119.8
C6—C5—C4	120.9 (5)	O5—C8—H8A	117.6
C7—C6—C5	119.9 (5)	C9—C8—H8A	117.6
C6—C7—C2	120.4 (5)	C14—C13—H13	120.7
O5—C8—C9	124.7 (5)	C12—C13—H13	120.7
C14—C9—C10	119.4 (5)	C13—C14—H14	119.3
C14—C9—C8	119.5 (5)	C9—C14—H14	119.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.84 (1)	1.99 (5)	2.631 (5)	133 (6)
O3—H3···O7ⁱ	0.84 (1)	2.04 (3)	2.816 (5)	153 (6)
O4—H4···O1ⁱⁱ	0.84 (1)	1.90 (3)	2.701 (5)	159 (6)
O6—H6···O5	0.84 (1)	1.87 (3)	2.653 (5)	154 (6)
O7—H7···O2	0.84 (1)	2.02 (3)	2.772 (5)	149 (6)
O8—H8···O5ⁱⁱⁱ	0.84 (1)	1.86 (2)	2.679 (5)	162 (7)

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

Experimental details

Crystal data
Chemical formula	C₇H₆O₄
M_r	154.12
Crystal system, space group	Monoclinic, Cc
Temperature (K)	100
a, b, c (Å)	3.6222 (3), 24.006 (2), 14.8965 (9)
β (°)	93.524 (5)
V (Å³)	1292.9 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.03 × 0.03

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5464, 1491, 1087
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.132, 1.01
No. of reflections	1491
No. of parameters	217
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32
Absolute structure	Friedel pairs were merged

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.84 (1)	1.99 (5)	2.631 (5)	133 (6)
O3—H3···O7ⁱ	0.84 (1)	2.04 (3)	2.816 (5)	153 (6)
O4—H4···O1ⁱⁱ	0.84 (1)	1.90 (3)	2.701 (5)	159 (6)
O6—H6···O5	0.84 (1)	1.87 (3)	2.653 (5)	154 (6)
O7—H7···O2	0.84 (1)	2.02 (3)	2.772 (5)	149 (6)
O8—H8···O5ⁱⁱⁱ	0.84 (1)	1.86 (2)	2.679 (5)	162 (7)

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

Acknowledgements

I thank the University of Malaya for supporting this study through the purchase of the diffractometer.

References

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