2,2′-Diisopropoxy-5,5′-methyl­enedi­benz­alde­hyde

Suresh, G.; Sabari, V.; Devaraj, A.; Bakthadoss, M.; Aravindhan, S.

doi:10.1107/S1600536812028048

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2199

https://doi.org/10.1107/S1600536812028048

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2,2′-Diisopropoxy-5,5′-methylenedibenzaldehyde

G. Suresh,^a V. Sabari,^a A. Devaraj,^b M. Bakthadoss ^b and S. Aravindhan ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^bDepartment of Organic Chemistry, University of Madras, Chennai 600 025, India
^*Correspondence e-mail: aravindhanpresidency@gmail.com

(Received 19 June 2012; accepted 20 June 2012; online 23 June 2012)

Molecules of the title compound, C₂₁H₂₄O₄, are located on a twofold rotation axis running through the central methylene C atom. The aldehyde group is coplanar with the benzene ring [C—C—C—O = 175.7 (4) °].

Related literature

For related salicylaldehyde compounds, see: Qiu et al. (2009 ); Yu et al. (2007 ); Wang et al. (2009 ).

Experimental

Crystal data

C₂₁H₂₄O₄
M_r = 340.40
Orthorhombic, F d d 2
a = 26.337 (9) Å
b = 28.349 (10) Å
c = 4.990 (2) Å
V = 3726 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.972, T_max = 0.984
4329 measured reflections
1022 independent reflections
886 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.114
S = 1.06
1022 reflections
114 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812028048/bt5945sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028048/bt5945Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028048/bt5945Isup3.cml

checkCIF report

Comment top

Salicylaldehyde and its derivatives are widely used in the construction of metal complexes (Qiu et al., 2009; Wang et al.,2009; Yu et al.,2007).

X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in (Fig. 1). There os one half molecule in the asymmetric unit located on a two-fold rotation axis. The aldehyde group is coplanar with the benzene ring [C2—C1—C8—O2 = 175.7 (4) °].

The crystal packing is stabilized by weak C-H···O hydrogen bonds.

Related literature top

For related salicylaldehyde compounds, see: Qiu et al. (2009); Yu et al. (2007); Wang et al. (2009).

Experimental top

To a stirred solution of 5,5'-methylenebis(2-hydroxybenzaldehyde) (0.50 g, 1.95 mmol) in CH₃CN (20 ml) was added K₂CO₃ (1.35 g, 9.76 mmol) and stirred for 15 min. To this, isopropylbromide (0.40 ml, 4.29 mmol) was added and stirred for 24 h at rt. After completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (15 ml) and extracted with ethyl acetate (3 × 15 ml). The combined organic layer was washed with brine (2 × 10 ml) and dried over anhydrous Na₂SO₄.The organic layer was concentrated and the solid thus obtained was washed with ethylacetate-hexanes (1:9) to afford the compound 5,5'-Methylenebis(2-isopropoxybenzaldehyde) as a colourless solid in 95% yield.

Structure description top

Salicylaldehyde and its derivatives are widely used in the construction of metal complexes (Qiu et al., 2009; Wang et al.,2009; Yu et al.,2007).

The crystal packing is stabilized by weak C-H···O hydrogen bonds.

For related salicylaldehyde compounds, see: Qiu et al. (2009); Yu et al. (2007); Wang et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 10% probability level.
	Fig. 2. A view of the crystal packing.

2,2'-Diisopropoxy-5,5'-methylenedibenzaldehyde top

Crystal data top

C₂₁H₂₄O₄	F(000) = 1456
M_r = 340.40	D_x = 1.214 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1022 reflections
a = 26.337 (9) Å	θ = 3.1–26.0°
b = 28.349 (10) Å	µ = 0.08 mm⁻¹
c = 4.990 (2) Å	T = 293 K
V = 3726 (2) Å³	Orthorhombic, colourless
Z = 8	0.35 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	1022 independent reflections
Radiation source: fine-focus sealed tube	886 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω and φ scans	θ_max = 26.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −32→32
T_min = 0.972, T_max = 0.984	k = −31→34
4329 measured reflections	l = −6→4

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0561P)² + 2.1412P] where P = (F_o² + 2F_c²)/3
1022 reflections	(Δ/σ)_max < 0.001
114 parameters	Δρ_max = 0.17 e Å⁻³
1 restraint	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₁H₂₄O₄	V = 3726 (2) Å³
M_r = 340.40	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 26.337 (9) Å	µ = 0.08 mm⁻¹
b = 28.349 (10) Å	T = 293 K
c = 4.990 (2) Å	0.35 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	1022 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	886 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.984	R_int = 0.035
4329 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.114	H-atom parameters constrained
S = 1.06	Δρ_max = 0.17 e Å⁻³
1022 reflections	Δρ_min = −0.13 e Å⁻³
114 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	Occ. (<1)
O1	0.15629 (6)	0.10388 (6)	0.7445 (5)	0.0632 (5)
C4	0.25293 (9)	0.18516 (9)	0.9981 (6)	0.0580 (6)
H4	0.2873	0.1919	0.9767	0.070*
C2	0.18085 (8)	0.13881 (8)	0.8776 (6)	0.0499 (6)
C7	0.2500	0.2500	1.3451 (9)	0.0711 (11)
H7A	0.2245	0.2642	1.4598	0.085*	0.50
H7B	0.2755	0.2358	1.4598	0.085*	0.50
C1	0.15181 (8)	0.16511 (8)	1.0577 (6)	0.0552 (7)
C3	0.23209 (8)	0.14955 (8)	0.8487 (6)	0.0572 (7)
H3	0.2521	0.1326	0.7288	0.069*
C5	0.22521 (9)	0.21160 (8)	1.1795 (5)	0.0546 (6)
C6	0.17461 (9)	0.20091 (8)	1.2046 (6)	0.0578 (7)
H6	0.1549	0.2182	1.3240	0.069*
C9	0.18476 (10)	0.06998 (9)	0.5895 (6)	0.0621 (7)
H9	0.2076	0.0865	0.4661	0.075*
O2	0.07084 (7)	0.17443 (8)	1.2544 (9)	0.1226 (13)
C10	0.21526 (11)	0.03853 (10)	0.7716 (8)	0.0760 (9)
H10A	0.2397	0.0571	0.8674	0.114*
H10B	0.2325	0.0151	0.6667	0.114*
H10C	0.1930	0.0233	0.8968	0.114*
C11	0.14556 (13)	0.04302 (12)	0.4324 (8)	0.0882 (11)
H11A	0.1274	0.0643	0.3176	0.132*
H11B	0.1222	0.0281	0.5537	0.132*
H11C	0.1620	0.0194	0.3255	0.132*
C8	0.09748 (9)	0.15523 (10)	1.0940 (10)	0.0888 (13)
H8	0.0828	0.1325	0.9845	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0503 (9)	0.0492 (9)	0.0902 (13)	−0.0024 (7)	0.0055 (10)	−0.0102 (10)
C4	0.0436 (11)	0.0618 (14)	0.0686 (15)	−0.0084 (10)	0.0086 (12)	0.0086 (14)
C2	0.0445 (11)	0.0388 (11)	0.0663 (15)	0.0025 (9)	0.0052 (12)	0.0066 (11)
C7	0.079 (2)	0.074 (3)	0.060 (2)	−0.0213 (19)	0.000	0.000
C1	0.0430 (11)	0.0383 (11)	0.0844 (19)	0.0028 (9)	0.0120 (13)	0.0036 (13)
C3	0.0477 (12)	0.0544 (14)	0.0695 (16)	−0.0004 (10)	0.0158 (12)	−0.0006 (14)
C5	0.0576 (12)	0.0495 (13)	0.0568 (15)	−0.0065 (10)	0.0027 (12)	0.0081 (12)
C6	0.0560 (12)	0.0444 (12)	0.0730 (18)	0.0018 (10)	0.0181 (13)	0.0005 (14)
C9	0.0704 (15)	0.0549 (14)	0.0609 (15)	−0.0082 (12)	0.0218 (14)	−0.0046 (13)
O2	0.0639 (12)	0.0834 (15)	0.221 (4)	−0.0002 (10)	0.0623 (19)	−0.031 (2)
C10	0.0793 (17)	0.0574 (15)	0.091 (2)	0.0121 (13)	0.0235 (18)	−0.0004 (17)
C11	0.098 (2)	0.082 (2)	0.084 (2)	−0.0235 (17)	0.011 (2)	−0.016 (2)
C8	0.0464 (13)	0.0554 (15)	0.164 (4)	0.0008 (12)	0.024 (2)	−0.018 (2)

Geometric parameters (Å, º) top

O1—C2	1.357 (3)	C5—C6	1.372 (3)
O1—C9	1.444 (3)	C6—H6	0.9300
C4—C3	1.370 (4)	C9—C10	1.505 (4)
C4—C5	1.384 (4)	C9—C11	1.505 (4)
C4—H4	0.9300	C9—H9	0.9800
C2—C3	1.391 (3)	O2—C8	1.196 (5)
C2—C1	1.396 (3)	C10—H10A	0.9600
C7—C5ⁱ	1.514 (4)	C10—H10B	0.9600
C7—C5	1.515 (4)	C10—H10C	0.9600
C7—H7A	0.9700	C11—H11A	0.9600
C7—H7B	0.9700	C11—H11B	0.9600
C1—C6	1.389 (3)	C11—H11C	0.9600
C1—C8	1.469 (3)	C8—H8	0.9300
C3—H3	0.9300

C2—O1—C9	120.03 (18)	C5—C6—H6	118.9
C3—C4—C5	122.9 (2)	C1—C6—H6	118.9
C3—C4—H4	118.5	O1—C9—C10	110.4 (3)
C5—C4—H4	118.5	O1—C9—C11	105.1 (2)
O1—C2—C3	124.9 (2)	C10—C9—C11	112.3 (2)
O1—C2—C1	116.35 (18)	O1—C9—H9	109.6
C3—C2—C1	118.8 (2)	C10—C9—H9	109.6
C5ⁱ—C7—C5	113.9 (4)	C11—C9—H9	109.6
C5ⁱ—C7—H7A	108.8	C9—C10—H10A	109.5
C5—C7—H7A	108.8	C9—C10—H10B	109.5
C5ⁱ—C7—H7B	108.8	H10A—C10—H10B	109.5
C5—C7—H7B	108.8	C9—C10—H10C	109.5
H7A—C7—H7B	107.7	H10A—C10—H10C	109.5
C6—C1—C2	119.6 (2)	H10B—C10—H10C	109.5
C6—C1—C8	119.7 (3)	C9—C11—H11A	109.5
C2—C1—C8	120.8 (2)	C9—C11—H11B	109.5
C4—C3—C2	119.6 (2)	H11A—C11—H11B	109.5
C4—C3—H3	120.2	C9—C11—H11C	109.5
C2—C3—H3	120.2	H11A—C11—H11C	109.5
C6—C5—C4	116.9 (2)	H11B—C11—H11C	109.5
C6—C5—C7	121.8 (2)	O2—C8—C1	124.6 (3)
C4—C5—C7	121.2 (2)	O2—C8—H8	117.7
C5—C6—C1	122.2 (2)	C1—C8—H8	117.7

C9—O1—C2—C3	9.8 (4)	C5ⁱ—C7—C5—C6	−122.2 (3)
C9—O1—C2—C1	−169.6 (2)	C5ⁱ—C7—C5—C4	58.8 (2)
O1—C2—C1—C6	178.9 (2)	C4—C5—C6—C1	0.4 (4)
C3—C2—C1—C6	−0.5 (4)	C7—C5—C6—C1	−178.6 (3)
O1—C2—C1—C8	−0.9 (4)	C2—C1—C6—C5	0.0 (4)
C3—C2—C1—C8	179.7 (3)	C8—C1—C6—C5	179.8 (3)
C5—C4—C3—C2	−0.1 (4)	C2—O1—C9—C10	68.9 (3)
O1—C2—C3—C4	−178.8 (2)	C2—O1—C9—C11	−169.7 (2)
C1—C2—C3—C4	0.6 (4)	C6—C1—C8—O2	−4.1 (6)
C3—C4—C5—C6	−0.4 (4)	C2—C1—C8—O2	175.7 (4)
C3—C4—C5—C7	178.7 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1	0.93	2.42	2.749 (3)	101

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄O₄
M_r	340.40
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	293
a, b, c (Å)	26.337 (9), 28.349 (10), 4.990 (2)
V (Å³)	3726 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.972, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	4329, 1022, 886
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.114, 1.06
No. of reflections	1022
No. of parameters	114
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

GS and SA thank Dr Babu Varghese, SAIF, IIT Madras, for the structure refinement clarifications and the Department of Bio Physics, University of Madras, for providing the single-crystal XRD facilities.

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Qiu, L., Lin, J. & Xu, Y. (2009). Inorg. Chem. Commun. 12, 986–989. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, H., Zhang, D., Ni, Z.-H., Li, X., Tian, L. & Jiang, J. (2009). Inorg. Chem. 48, 5946–5956. Web of Science CSD CrossRef PubMed CAS Google Scholar
Yu, T.-Z., Su, W.-M., Li, W.-L., Hong, Z.-R., Hua, R.-N. & Li, B. (2007). Thin Solid Films, 515, 4080–4084. Web of Science CrossRef CAS Google Scholar