A combined crystallographic, thermal, Raman and computational study on polymorphism and phase transition in 1-(4-hex­yloxy-3-hy­droxy­phen­yl)ethanone

Suárez, S.; Manzano, V.E.; Fantoni, A.C.; Halac, E.; Baggio, R.; Cukiernik, F.D.

doi:10.1107/S2053229617016795

A combined crystallographic, thermal, Raman and computational study on polymorphism and phase transition in 1-(4-hexyloxy-3-hydroxyphenyl)ethanone

S. Suárez, V. E. Manzano, A. C. Fantoni, E. Halac, R. Baggio and F. D. Cukiernik

The crystal structure of the triclinic polymorph of 1-(4-hexyloxy-3-hydroxyphenyl)ethanone, C₁₄H₂₀O₃, differs markedly from that of the orthorhombic polymorph [Manzano et al. (2015). Acta Cryst. C71, 1022–1027]. The two molecular structures are alike with respect to their bond lengths and angles, but differ in their spatial arrangement. This gives rise to quite different packing schemes, even if built up by similar chains having the hydroxy–ethanone O—H

O hydrogen-bond synthon in common. Both phases were found to be related by a first-order thermally driven phase transformation at 338–340 K, which is discussed in detail. The relative stabilities of both polymorphs are explained on the basis of both the noncovalent interactions operating in each structure and quantum chemical calculations. The polymorphic phase transition has also been studied experimentally by means of differential scanning calorimetry (DSC) experiments, conducted on individual single crystals, Raman spectroscopy and controlled heating under a microscope of individual single crystals, which were further characterized by powder and single-crystal X-ray diffraction.

Keywords: phase transformation; DSC; Raman; powder diffraction; crystal structure; ethanone; computational chemistry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617016795/fn3250sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229617016795/fn3250Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229617016795/fn3250sup3.pdf Raman diagrams
	AVI file https://doi.org/10.1107/S2053229617016795/fn3250sup4.avi A short video of the phase transformation as seen in the heating stage of the microscope

CCDC reference: 1586950

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

1-(4-Hexyloxy-3-hydroxyphenyl)ethanone top

Crystal data top

C₁₄H₂₀O₃	Z = 2
M_r = 236.30	F(000) = 256
Triclinic, P1	D_x = 1.225 Mg m⁻³
a = 7.9565 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5027 (3) Å	Cell parameters from 1556 reflections
c = 11.0842 (3) Å	θ = 3.6–27.2°
α = 77.857 (3)°	µ = 0.09 mm⁻¹
β = 76.632 (3)°	T = 100 K
γ = 62.158 (4)°	Block, colourless
V = 640.51 (4) Å³	0.25 × 0.18 × 0.12 mm

Data collection top

Oxford Diffraction Xcalibur Eos CCD Gemini diffractometer	2612 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.046
thick slices scans	θ_max = 29.2°, θ_min = 3.2°
Absorption correction: multi-scan CrysAlisPro (Oxford Diffraction, 2009)	h = −10→10
	k = −11→11
28336 measured reflections	l = −14→15
3221 independent reflections

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0631P)² + 0.1165P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3221 reflections	Δρ_max = 0.32 e Å⁻³
160 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O1	0.69662 (12)	−0.45366 (10)	1.22449 (7)	0.0278 (2)
O2	0.71022 (11)	0.21100 (10)	1.30669 (7)	0.02086 (18)
H2'	0.711 (2)	0.3047 (16)	1.2645 (14)	0.049 (5)*
O3	0.74126 (11)	0.28644 (9)	1.05800 (6)	0.02038 (18)
C1	0.71464 (14)	−0.18616 (13)	1.22687 (9)	0.0173 (2)
C2	0.72667 (15)	−0.14790 (13)	1.09743 (9)	0.0193 (2)
H2	0.7276	−0.2279	1.0513	0.023*
C3	0.73724 (15)	0.00817 (13)	1.03673 (9)	0.0192 (2)
H3	0.7469	0.0317	0.9502	0.023*
C4	0.73342 (14)	0.12918 (13)	1.10527 (9)	0.0167 (2)
C5	0.71911 (14)	0.09337 (13)	1.23648 (9)	0.0163 (2)
C6	0.71257 (14)	−0.06435 (13)	1.29536 (9)	0.0172 (2)
H6	0.7067	−0.0899	1.3816	0.021*
C7	0.70277 (14)	−0.35488 (13)	1.28766 (9)	0.0193 (2)
C8	0.69610 (16)	−0.40170 (14)	1.42693 (10)	0.0236 (2)
H8A	0.7007	−0.5188	1.4506	0.035*
H8B	0.5791	−0.3154	1.4683	0.035*
H8C	0.8043	−0.4008	1.4507	0.035*
C9	0.75757 (15)	0.33686 (13)	0.92465 (9)	0.0187 (2)
H9A	0.6451	0.3531	0.8940	0.022*
H9B	0.8711	0.2462	0.8818	0.022*
C10	0.77289 (15)	0.51108 (13)	0.90520 (9)	0.0186 (2)
H10A	0.8869	0.4897	0.9364	0.022*
H10B	0.6624	0.5952	0.9548	0.022*
C11	0.78321 (15)	0.59723 (13)	0.77035 (9)	0.0184 (2)
H11A	0.6697	0.6202	0.7378	0.022*
H11B	0.8951	0.5160	0.7198	0.022*
C12	0.79613 (15)	0.77313 (13)	0.76227 (9)	0.0192 (2)
H12A	0.6864	0.8505	0.8163	0.023*
H12B	0.9111	0.7476	0.7942	0.023*
C13	0.80149 (15)	0.87433 (14)	0.63198 (9)	0.0215 (2)
H13A	0.6882	0.8985	0.5986	0.026*
H13B	0.9136	0.7996	0.5780	0.026*
C14	0.80867 (16)	1.05053 (14)	0.63071 (10)	0.0246 (2)
H14A	0.7011	1.1229	0.6868	0.037*
H14B	0.8033	1.1130	0.5477	0.037*
H14C	0.9261	1.0267	0.6568	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0445 (5)	0.0198 (4)	0.0255 (4)	−0.0195 (4)	−0.0064 (3)	−0.0014 (3)
O2	0.0347 (4)	0.0162 (4)	0.0167 (4)	−0.0148 (3)	−0.0064 (3)	−0.0004 (3)
O3	0.0338 (4)	0.0167 (4)	0.0149 (3)	−0.0157 (3)	−0.0039 (3)	0.0010 (3)
C1	0.0183 (5)	0.0147 (5)	0.0194 (5)	−0.0081 (4)	−0.0029 (4)	−0.0012 (4)
C2	0.0248 (5)	0.0166 (5)	0.0197 (5)	−0.0108 (4)	−0.0038 (4)	−0.0039 (4)
C3	0.0260 (5)	0.0185 (5)	0.0148 (4)	−0.0112 (4)	−0.0038 (4)	−0.0010 (4)
C4	0.0201 (5)	0.0138 (5)	0.0173 (5)	−0.0092 (4)	−0.0030 (4)	0.0007 (4)
C5	0.0181 (5)	0.0150 (5)	0.0174 (5)	−0.0078 (4)	−0.0034 (4)	−0.0034 (4)
C6	0.0205 (5)	0.0163 (5)	0.0149 (4)	−0.0085 (4)	−0.0038 (4)	−0.0003 (4)
C7	0.0213 (5)	0.0154 (5)	0.0216 (5)	−0.0088 (4)	−0.0032 (4)	−0.0013 (4)
C8	0.0316 (6)	0.0189 (5)	0.0214 (5)	−0.0139 (4)	−0.0036 (4)	0.0014 (4)
C9	0.0252 (5)	0.0190 (5)	0.0136 (5)	−0.0122 (4)	−0.0024 (4)	0.0003 (4)
C10	0.0239 (5)	0.0175 (5)	0.0166 (5)	−0.0116 (4)	−0.0033 (4)	0.0001 (4)
C11	0.0219 (5)	0.0178 (5)	0.0160 (5)	−0.0101 (4)	−0.0021 (4)	−0.0007 (4)
C12	0.0230 (5)	0.0188 (5)	0.0172 (5)	−0.0115 (4)	−0.0032 (4)	0.0008 (4)
C13	0.0252 (5)	0.0223 (5)	0.0162 (5)	−0.0119 (4)	−0.0014 (4)	0.0011 (4)
C14	0.0253 (5)	0.0210 (5)	0.0254 (5)	−0.0114 (4)	−0.0034 (4)	0.0041 (4)

Geometric parameters (Å, º) top

O1—C7	1.2247 (13)	C9—C10	1.5092 (14)
O2—C5	1.3589 (12)	C9—H9A	0.9700
O2—H2'	0.836 (9)	C9—H9B	0.9700
O3—C4	1.3543 (12)	C10—C11	1.5219 (13)
O3—C9	1.4429 (11)	C10—H10A	0.9700
C1—C2	1.3939 (14)	C10—H10B	0.9700
C1—C6	1.3994 (14)	C11—C12	1.5292 (14)
C1—C7	1.4871 (13)	C11—H11A	0.9700
C2—C3	1.3868 (14)	C11—H11B	0.9700
C2—H2	0.9300	C12—C13	1.5202 (13)
C3—C4	1.3877 (14)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.4109 (14)	C13—C14	1.5227 (15)
C5—C6	1.3814 (13)	C13—H13A	0.9700
C6—H6	0.9300	C13—H13B	0.9700
C7—C8	1.5058 (14)	C14—H14A	0.9600
C8—H8A	0.9600	C14—H14B	0.9600
C8—H8B	0.9600	C14—H14C	0.9600
C8—H8C	0.9600

C5—O2—H2'	113.3 (12)	C10—C9—H9B	110.8
C4—O3—C9	119.06 (8)	H9A—C9—H9B	108.9
C2—C1—C6	119.09 (9)	C9—C10—C11	115.00 (8)
C2—C1—C7	118.71 (9)	C9—C10—H10A	108.5
C6—C1—C7	122.20 (9)	C11—C10—H10A	108.5
C3—C2—C1	120.73 (9)	C9—C10—H10B	108.5
C3—C2—H2	119.6	C11—C10—H10B	108.5
C1—C2—H2	119.6	H10A—C10—H10B	107.5
C2—C3—C4	119.90 (9)	C10—C11—C12	110.35 (8)
C2—C3—H3	120.0	C10—C11—H11A	109.6
C4—C3—H3	120.0	C12—C11—H11A	109.6
O3—C4—C3	125.89 (9)	C10—C11—H11B	109.6
O3—C4—C5	114.05 (8)	C12—C11—H11B	109.6
C3—C4—C5	120.05 (9)	H11A—C11—H11B	108.1
O2—C5—C6	119.07 (9)	C13—C12—C11	115.10 (9)
O2—C5—C4	121.58 (9)	C13—C12—H12A	108.5
C6—C5—C4	119.35 (9)	C11—C12—H12A	108.5
C5—C6—C1	120.85 (9)	C13—C12—H12B	108.5
C5—C6—H6	119.6	C11—C12—H12B	108.5
C1—C6—H6	119.6	H12A—C12—H12B	107.5
O1—C7—C1	119.89 (9)	C12—C13—C14	112.55 (9)
O1—C7—C8	120.53 (9)	C12—C13—H13A	109.1
C1—C7—C8	119.57 (9)	C14—C13—H13A	109.1
C7—C8—H8A	109.5	C12—C13—H13B	109.1
C7—C8—H8B	109.5	C14—C13—H13B	109.1
H8A—C8—H8B	109.5	H13A—C13—H13B	107.8
C7—C8—H8C	109.5	C13—C14—H14A	109.5
H8A—C8—H8C	109.5	C13—C14—H14B	109.5
H8B—C8—H8C	109.5	H14A—C14—H14B	109.5
O3—C9—C10	104.79 (8)	C13—C14—H14C	109.5
O3—C9—H9A	110.8	H14A—C14—H14C	109.5
C10—C9—H9A	110.8	H14B—C14—H14C	109.5
O3—C9—H9B	110.8

C6—C1—C2—C3	0.25 (15)	C4—C5—C6—C1	−1.77 (15)
C7—C1—C2—C3	179.74 (9)	C2—C1—C6—C5	1.06 (15)
C1—C2—C3—C4	−0.82 (16)	C7—C1—C6—C5	−178.42 (9)
C9—O3—C4—C3	−0.85 (15)	C2—C1—C7—O1	−2.66 (15)
C9—O3—C4—C5	179.52 (8)	C6—C1—C7—O1	176.81 (10)
C2—C3—C4—O3	−179.50 (9)	C2—C1—C7—C8	178.05 (9)
C2—C3—C4—C5	0.10 (16)	C6—C1—C7—C8	−2.48 (15)
O3—C4—C5—O2	1.30 (14)	C4—O3—C9—C10	−177.13 (8)
C3—C4—C5—O2	−178.35 (9)	O3—C9—C10—C11	−177.50 (8)
O3—C4—C5—C6	−179.17 (8)	C9—C10—C11—C12	179.39 (8)
C3—C4—C5—C6	1.19 (15)	C10—C11—C12—C13	−178.34 (8)
O2—C5—C6—C1	177.78 (9)	C11—C12—C13—C14	178.39 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2′···O3	0.84 (1)	2.28 (2)	2.6758 (10)	110 (1)
O2—H2′···O1ⁱ	0.84 (1)	1.96 (1)	2.7634 (10)	160 (2)

Symmetry code: (i) x, y+1, z.

Experimental details for (I) and (II). top

	(I) (This work)	(II) (Manzano et al., 2015)
Crystal system, space group	Triclinic, P1	Orthorhombic, Pbca
Temperature (K)	100	170
a, b, c (Å)	7.9565 (3), 8.5027 (3), 11.0842 (3)	19.3847 (10), 9.0716 (4), 30.3953 (12)
α, β, γ (°)	77.857 (3), 76.632 (3), 62.158 (4)	90, 90, 90
V (Å³)	640.51 (4)	5345.0 (4)
Z	2	16
µ (mm^-1)	0.09	0.08
Crystal size (mm)	0.25 × 0.18 × 0.12	0.32 × 0.26 × 0.18
No. of measured, independent and observed [I > 2σ(I)] reflections	28336, 3221, 2612	18445, 6210, 3357
R_int	0.046	0.058
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.111, 1.02	0.065, 0.186, 1.00
No. of reflections	3221	6210
No. of parameters	160	365
No. of restraints	1	12
Δρ_max, Δρ_min (e Å^-3)	0.32, -0.23	0.32, -0.27

Common to both determinations: Chemical formula: C₁₄H₂₀O₃; M_r 236.30; Radiation: Mo Kα; Diffractometer: Oxford Diffraction Xcalibur CCD Eos Gemini; Absorption correction: Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009); H-atom treatment: treated by a mixture of independent and constrained refinement.

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008), SHELXL97, PLATON (Spek, 2009).

Selected torsion angles (°) top

	(I)	(II)	Code
C6—C1—C2—C3	0.25 (15)	-1.2 (4)	*
C7—C1—C2—C3	179.74 (9)	177.8 (2)	*
C1—C2—C3—C4	-0.82 (16)	0.6 (4)	*
C9—O3—C4—C3	-0.85 (15)	-0.3 (3)	*
C9—O3—C4—C5	179.52 (8)	179.26 (18)	*
C2—C3—C4—O3	-179.50 (9)	-179.2 (2)	*
C2—C3—C4—C5	0.10 (16)	1.3 (3)	*
O3—C4—C5—O2	1.30 (14)	0.2 (3)	*
C3—C4—C5—O2	-178.35 (9)	179.8 (2)	*
O3—C4—C5—C6	-179.17 (8)	177.92 (19)	*
C3—C4—C5—C6	1.19 (15)	-2.5 (3)	*
O2—C5—C6—C1	177.78 (9)	179.66 (19)	*
C4—C5—C6—C1	-1.76 (15)	1.9 (3)	*
C2—C1—C6—C5	1.06 (15)	0.0 (3)	*
C7—C1—C6—C5	-178.42 (9)	-179.0 (2)	*
C4—O3—C9—C10	-177.13 (8)	173.43 (18)	**
C9—C10—C11—C12	179.39 (8)	-171.0 (2)	**
C10—C11—C12—C13	-178.34 (8)	176.9 (2)	**
C11—C12—C13—C14	178.39 (8)	179.7 (2)	**
C2—C1—C7—O1	-2.66 (15)	-169.7 (2)	***
C6—C1—C7—O1	176.81 (10)	9.3 (3)	***
C2—C1—C7—C8	178.05 (9)	11.5 (3)	***
C6—C1—C7—C8	-2.48 (15)	-169.5 (2)	***
O3—C9—C10—C11	-177.50 (8)	-65.7 (3)	****

For code definition, see text.

Hydrogen-bond geometry for (I) and (II) (Å, °)
Cg1 is the centroid of the C1–C6 ring. top

	D—H···A	D—H	H···A	D···A	D—H···A
(I)	O2A—H2OA···O1B	0.95 (3)	1.83 (3)	2.735 (2)	157 (2)
	O2B—H2OB···O1Aⁱ	0.92 (3)	1.89 (3)	2.779 (2)	162 (3)
(II)	O2—H2'···O1ⁱ	0.84 (1)	1.96 (1)	2.7634 (10)	160 (2)
	C9—H9B···Cg1ⁱⁱ	0.97	2.85	3.7422 (13)	153
	C12—H12A···Cg1ⁱⁱⁱ	0.97	2.86	3.6436 (13)	138

Symmetry code for (I): (i) x, -y+1/2, z-1/2. Symmetry codes for (II): (i) x, y+1, z; (ii) -x+2, -y, -z+2; (iii) -x+1, -y+1, -z+2.

Comaparative thermal expansion of the units cells in (I) and (II) [What is intended for the units of Δ?] top

		(I)			(II)
	100 K	295 K	Δ (^°/_°°)	170 K	295 K	Δ (^°/_°°)
a	19.3847 (10)	19.8299 (10)	23	7.9565 (3)	8.14 (2)	24
b	9.0716 (4)	9.1277 (4)	6	8.5027 (3)	8.52 (2)	3 *
c	30.3953 (12)	30.4885 (12)	3 *	11.0842 (3)	11.25 (3)	15
α	90	90		77.857 (3)	76.4 (2)
β	90	90		76.632 (3)	77.3 (2)
γ	90	90		62.158 (4)	63.0 (3)
Volume	5345.0 (4)	5518.5 (4)	32	640.51 (4)	670 (3)	46

Note: (*) chain direction.

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A combined crystallographic, thermal, Raman and computational study on polymorphism and phase transition in 1-(4-hex­yloxy-3-hy­droxy­phen­yl)ethanone

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A combined crystallographic, thermal, Raman and computational study on polymorphism and phase transition in 1-(4-hexyloxy-3-hydroxyphenyl)ethanone