Redetermination of 4-hydroxy­benzaldehyde

Jasinski, J.P.; Butcher, R.J.; Narayana, B.; Swamy, M.T.; Yathirajan, H.S.

doi:10.1107/S1600536807063659

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o187

https://doi.org/10.1107/S1600536807063659

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Redetermination of 4-hydroxybenzaldehyde

Jerry P. Jasinski,^a ^* Ray J. Butcher,^b B. Narayana,^c M. T. Swamy ^d and H. S. Yathirajan ^e

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574199, India, ^dDepartment Chemistry, Sambhram Institute of Technology, Bangalore 560 097, India, and ^eDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570006, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 22 November 2007; accepted 27 November 2007; online 6 December 2007)

This is a redetermination of the structure of the title compound, C₇H₆O₂, which was first reported by Iwasaki [Acta Cryst. (1977 ), B33, 1646–1648]. The results are obtained with greater precision in the present study. Crystal packing is stabilized by intermolecular O—H⋯O interactions between the hydroxyl and aldehyde groups which link the molecules into chains in a zigzag pattern along the [110] plane of the unit cell.

Related literature

For the previous structure determination, see: Iwasaki (1977). Forrelated structures, see: Matos Beja et al. (1997 , 2000 ); Paixão et al. (2000 ); Silva et al. (2004 ). For related literature, see: Antonucci (1978 ); Bigi et al. (1999 ); Dean (1963 ); Samal et al. (1999 ).

Experimental

Crystal data

C₇H₆O₂
M_r = 122.12
Monoclinic, P 2₁ /c
a = 6.6992 (8) Å
b = 13.5550 (12) Å
c = 7.1441 (11) Å
β = 112.871 (16)°
V = 597.74 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 (2) K
0.49 × 0.37 × 0.24 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlisPro (Version 171.31.8) and CrysAlis RED (Version 1.171.31.8). Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.949, T_max = 0.970
3559 measured reflections
1170 independent reflections
841 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.117
S = 1.06
1170 reflections
86 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82 (3)	1.92 (3)	2.731 (2)	171 (2)
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlisPro (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlisPro (Version 171.31.8) and CrysAlis RED (Version 1.171.31.8). Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063659/lx2042sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063659/lx2042Isup2.hkl

checkCIF report

Comment top

The title compound, 4-hydroxy benzaldehyde (Fig. 1) is used in the preparation of aldehyde methacrylates and finds application in the manufacture of dental materials which can form strong and durable bonds with dentin (Antonucci, 1978). It is used in the preparation of benzopyrans and have wide applications in the perfume, cosmetic and pharmaceutical industry (Dean, 1963; Bigi et al., 1999). They are also used in the preparation of chelating resins (Samal et al., 1999).

The crystal structures of p-hydroxybenzaldehyde (Iwasaki, 1977), 2-bromo-5-hydroxybenzaldehyde (Matos Beja et al., 2000), a new polymorph of 2-bromo-5-hydroxybenzaldehyde (Silva et al., 2004), 3-hydroxybenzaldehyde (Paixão et al., 2000) and 2,4-dibromo-5-hydroxybenzaldehyde, (Matos Beja et al., 1997) have been reported. In view of the importance of the title compound in the pharmaceutical industry, this paper reports a redetermination of the crystal structure with greater precision and accuracy. Crystal packing is stabilized by intermolecular O—H···O interactions between the hydroxyl and aldlehyde groups which link the molecules into chains in a zigzag pattern along the [110] plane of the unit cell (Fig. 2).

Related literature top

For related structures, see: Matos Beja et al. (1997, 2000); Iwasaki (1977); Paixão et al. (2000); Silva et al. (2004). For related literature, see: Antonucci (1978); Bigi et al. (1999); Dean (1963); Samal et al. (1999).

Experimental top

A sample of 4-hydroxybenzaldehyde was obtained from Sigma–Aldrich and was recrystallized from ethylacetate by slow evaporation to obtain good quality crystals (m.p.: 385–387 K).

Structure description top

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. ORTEP view of the title compound, showing the atom numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. The molecular packing for the title compound viewed down the c axis. Dashed lines indicate C—H···O intermolecular hydrogen bonds.

4-Hydroxybenzaldehyde top

Crystal data top

C₇H₆O₂	F(000) = 256
M_r = 122.12	D_x = 1.357 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 385–387 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.6992 (8) Å	Cell parameters from 1669 reflections
b = 13.5550 (12) Å	θ = 5.3–29.0°
c = 7.1441 (11) Å	µ = 0.10 mm⁻¹
β = 112.871 (16)°	T = 296 K
V = 597.74 (15) Å³	Chunk, colourless
Z = 4	0.49 × 0.37 × 0.24 mm

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	1170 independent reflections
Radiation source: fine-focus sealed tube	841 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 10.5081 pixels mm^-1	θ_max = 26.0°, θ_min = 5.5°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −15→16
T_min = 0.949, T_max = 0.970	l = −8→8
3559 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.068P)²] where P = (F_o² + 2F_c²)/3
1170 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₇H₆O₂	V = 597.74 (15) Å³
M_r = 122.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6992 (8) Å	µ = 0.10 mm⁻¹
b = 13.5550 (12) Å	T = 296 K
c = 7.1441 (11) Å	0.49 × 0.37 × 0.24 mm
β = 112.871 (16)°

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	1170 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	841 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.970	R_int = 0.022
3559 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.13 e Å⁻³
1170 reflections	Δρ_min = −0.18 e Å⁻³
86 parameters

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
O1	0.1345 (2)	0.72809 (8)	0.1335 (2)	0.0652 (4)
H1	0.016 (4)	0.7359 (17)	0.140 (3)	0.092 (8)*
O2	0.2691 (2)	0.26982 (8)	0.3786 (2)	0.0633 (4)
C1	0.1834 (2)	0.63218 (11)	0.1834 (2)	0.0458 (4)
C2	0.3718 (2)	0.59530 (11)	0.1700 (2)	0.0499 (4)
H2	0.4587	0.6359	0.1284	0.060*
C3	0.4277 (2)	0.49829 (11)	0.2187 (2)	0.0465 (4)
H3	0.5542	0.4740	0.2112	0.056*
C4	0.2990 (2)	0.43542 (11)	0.2793 (2)	0.0417 (4)
C5	0.1100 (2)	0.47379 (11)	0.2921 (2)	0.0452 (4)
H5	0.0218	0.4330	0.3317	0.054*
C6	0.0543 (2)	0.57089 (11)	0.2467 (2)	0.0470 (4)
H6	−0.0698	0.5959	0.2581	0.056*
C7	0.3667 (3)	0.33405 (12)	0.3294 (2)	0.0509 (4)
H7	0.4981	0.3161	0.3235	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0635 (8)	0.0422 (7)	0.1018 (10)	0.0034 (6)	0.0451 (7)	0.0091 (6)
O2	0.0586 (7)	0.0434 (7)	0.0917 (9)	−0.0019 (5)	0.0332 (7)	0.0049 (6)
C1	0.0463 (8)	0.0385 (8)	0.0547 (9)	−0.0030 (6)	0.0219 (7)	−0.0039 (7)
C2	0.0472 (9)	0.0463 (9)	0.0636 (10)	−0.0078 (7)	0.0297 (8)	−0.0039 (7)
C3	0.0372 (7)	0.0483 (9)	0.0582 (9)	−0.0026 (6)	0.0231 (7)	−0.0089 (7)
C4	0.0396 (8)	0.0404 (8)	0.0447 (8)	−0.0013 (6)	0.0157 (6)	−0.0058 (6)
C5	0.0417 (8)	0.0450 (9)	0.0536 (9)	−0.0050 (7)	0.0235 (7)	−0.0012 (7)
C6	0.0404 (8)	0.0466 (9)	0.0593 (9)	0.0020 (7)	0.0252 (7)	−0.0018 (7)
C7	0.0430 (8)	0.0455 (9)	0.0648 (10)	−0.0012 (7)	0.0217 (8)	−0.0055 (7)

Geometric parameters (Å, º) top

O1—C1	1.354 (2)	C3—H3	0.9300
O1—H1	0.82 (3)	C4—C5	1.404 (2)
O2—C7	1.219 (2)	C4—C7	1.448 (2)
C1—C2	1.395 (2)	C5—C6	1.372 (2)
C1—C6	1.395 (2)	C5—H5	0.9300
C2—C3	1.374 (2)	C6—H6	0.9300
C2—H2	0.9300	C7—H7	0.9300
C3—C4	1.395 (2)

C1—O1—H1	104.4 (16)	C3—C4—C7	118.98 (13)
O1—C1—C2	117.30 (14)	C5—C4—C7	122.62 (13)
O1—C1—C6	122.68 (14)	C6—C5—C4	120.61 (13)
C2—C1—C6	120.02 (14)	C6—C5—H5	119.7
C3—C2—C1	119.35 (14)	C4—C5—H5	119.7
C3—C2—H2	120.3	C5—C6—C1	120.12 (14)
C1—C2—H2	120.3	C5—C6—H6	119.9
C2—C3—C4	121.50 (14)	C1—C6—H6	119.9
C2—C3—H3	119.3	O2—C7—C4	126.70 (15)
C4—C3—H3	119.3	O2—C7—H7	116.7
C3—C4—C5	118.39 (13)	C4—C7—H7	116.7

O1—C1—C2—C3	−179.85 (14)	C7—C4—C5—C6	178.77 (14)
C6—C1—C2—C3	0.3 (2)	C4—C5—C6—C1	1.2 (2)
C1—C2—C3—C4	0.7 (2)	O1—C1—C6—C5	178.90 (14)
C2—C3—C4—C5	−0.8 (2)	C2—C1—C6—C5	−1.2 (2)
C2—C3—C4—C7	−179.78 (14)	C3—C4—C7—O2	−177.67 (15)
C3—C4—C5—C6	−0.2 (2)	C5—C4—C7—O2	3.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82 (3)	1.92 (3)	2.731 (2)	171 (2)

Symmetry code: (i) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₆O₂
M_r	122.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	6.6992 (8), 13.5550 (12), 7.1441 (11)
β (°)	112.871 (16)
V (Å³)	597.74 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.49 × 0.37 × 0.24

Data collection
Diffractometer	Oxford Diffraction Gemini R CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.949, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	3559, 1170, 841
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.117, 1.06
No. of reflections	1170
No. of parameters	86
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.18

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82 (3)	1.92 (3)	2.731 (2)	171 (2)

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

MTS thanks the Sambhram Institute of Technology for the use of their research facilities. RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the X-ray diffractometer.

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