Triclinic polymorph of 4-[4-(4-formyl­phen­oxy)but­oxy]benzaldehyde

Tomislav Balić; Berislav Marković; Ivana Balić

doi:10.1107/S1600536812050994

. 2012 Dec 22;69(Pt 1):o126. doi: 10.1107/S1600536812050994

Triclinic polymorph of 4-[4-(4-formylphenoxy)butoxy]benzaldehyde

Tomislav Balić ^a,^*, Berislav Marković ^a, Ivana Balić ^a

PMCID: PMC3588312 PMID: 23476387

Abstract

The title compound, C₁₈H₁₈O₄, is a triclinic polymorph of the previously reported monoclinic polymorph [Han & Zhen (2005 ▶). Acta Cryst. E61, o4358–o4359]. In the crystal of the triclinic polymorph, molecules are linked by two pairs of C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (102), and enclosing loops with graph set motifs of R ₂ ²(8) and R ₂ ²(6).

Related literature

For the monoclinic polymorph, see: Han & Zhen (2005 ▶). For related structures and the synthesis of similar compounds, see: Balić et al. (2012 ▶); Ma & Cao (2011 ▶); Dehno Khalaji et al. (2011 ▶); Narasimha Moorthy et al. (2005 ▶); Ilhan et al. (2007 ▶). For graph-set analysis of hydrogen bonds, see Bernstein et al. (1995 ▶). graphic file with name e-69-0o126-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₈O₄
M _r = 298.32
Triclinic,
a = 4.4969 (2) Å
b = 7.9507 (6) Å
c = 11.0679 (8) Å
α = 73.854 (6)°
β = 84.788 (5)°
γ = 80.903 (5)°
V = 374.86 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 190 K
0.59 × 0.35 × 0.21 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.683, T _max = 1.000
2235 measured reflections
1473 independent reflections
1272 reflections with I > 2σ(I)
R _int = 0.010

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.123
S = 1.04
1473 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶), PARST97 (Nardelli, 1995 ▶) and Mercury (Macrae et al., 2006 ▶).

Supplementary Material

Click here for additional data file.^{(14.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812050994/ng5308sup1.cif

e-69-0o126-sup1.cif^{(14.2KB, cif)}

Click here for additional data file.^{(72.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050994/ng5308Isup2.hkl

e-69-0o126-Isup2.hkl^{(72.6KB, hkl)}

Click here for additional data file.^{(5.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812050994/ng5308Isup3.cml

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
C6—H6⋯O2ⁱ	0.95	2.58	3.4985 (16)	162
C1—H1⋯O1ⁱⁱ	0.95	2.59	3.3953 (18)	143

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Ministry of Science, Education and Sports of the Republic of Croatia (grant No. 119–1193079-1084). The authors wish to thank Professor Dubravka Matković-Čalogović for help with the crystallography.

supplementary crystallographic information

Comment

Reacent structural studies of dialdehydes (Balić et al. 2012; Narasimha Moorthy et al. 2005), or the so called two-arm aldehydes have proposed them as potential precursors for condensation reactions with primary amines (Ilhan et al. 2007; Ma & Cao 2011; Dehno Khalaji et al. 2011). In a relation to this structural studies a new triclinic polymorph of title compound was found. Previously reported monoclinic polymorph (Han & Zhen 2005) was reported in P2₁/c space group with Z=2. The new polymorph was found in P1 space group (Z=1), with different intermolecular interactions (Figure 1.).

The original polymorph crystallize in monoclinic space group P2₁/c, with a = 7.988 (2), b = 6.6635 (16), c= 14.260 (4) Å, β= 96.354 (4)° and Z = 2 (Han & Zhen 2005). The title compound crystallizes in the space group P1 with a = 4.5749 (7), b= 7.9467 (10), c = 14.260 (4) Å, α= 73.597 (11)°, β = 83.154 (11)°, γ = 80.533 (12)° and Z = 1. In the reported structure crystallographic inversion centre lies in the center of the molecule, so the asymmetric unit comprises only one half of the molecule. The molecular structure of the title compound is shown in Figure 2. In the triclinic polymorph the molecules are linked in centrosymetric dimers via weak C1— H1···O1 intermolecular interactions, as previously reported by Narasimha Moorthy et al. (2005) and Balić et al. (2012). Additional stabilization of crystal structure is accomplished by weak C4— H4···O2 (Figure 1.). In the previously reported monoclinic polymorph the dihedral angle between benzaldehyde group and four central carbon atoms is 62.82°, while in triclinic polymorph this angle is 42.07°. However, the largest difference between these two polymorphs is manifested by the presence of R²₂(6) and R²₂(8) (Bernstein et al. 1995) supramolecular motifs in the triclinic polymorph.

Experimental

The title compound was prepared by folowing procedure: p-hydroxybenzaldehyde (50 mmol) and K₂CO₃ (50 mmol) were mixed in DMF and the mixture was brought to brisk reflux. 25 mmol of butane-1,4-dibrom dissolved in DMF was then added and the reaction mixture was refluxed for 5 h. After the reaction was complete, 100 ml of water was added and the resulting percipitate was filtered and washed with water. Single crystals suitable for X-ray diffraction were grown via slow evaporation from ethanol solution of the title compound.