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X-ray powder diffraction patterns of n-butanol at 110 K and the isothermal transformation above the glass transition temperature of the supercooled liquid into the glacial state were recorded with a laboratory diffractometer. The starting structural model of the crystalline stable phase was found by a Monte-Carlo simulated annealing method. The final structure was obtained through Rietveld refinements with soft restraints on the interatomic bond lengths and angles. The cell is triclinic with space group P1 and contains two molecules. The width of the Bragg peaks is interpreted by a phenomenological microstructural approach in terms of anisotropic strain effects. The study of the hydrogen bonds by Raman spectroscopy shows the existence of two main kinds of hydrogen bonds in the crystal, in agreement with the structure obtained by diffraction. The glacial state resulting from an abortive crystallization is composed of microcrystallites of the stable phase coexisting with non-transformed supercooled liquid. Crystalline features of the glacial state were determined as closely connected to the microstructural description of the crystal, leading to information about the origin of the glacial state.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052519213004843/ps5021sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052519213004843/ps5021Isup2.hkl
Contains datablock I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052519213004843/ps5021Isup3.rtv
Contains datablock I

Computing details top

Data collection: SYMPHONIX; program(s) used to solve structure: FOX; program(s) used to refine structure: FULLPROF; molecular graphics: ORTEP-3; software used to prepare material for publication: SHELX97 and PARST.

Figures top
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[Figure 9]
(I) top
Crystal data top
C4H10OV = 239.59 (1) Å3
Mr = 74.12Z = 2
Triclinic, P1F(000) = 84.0
Hall symbol: P 1Dx = 1.027 Mg m3
a = 5.10141 (12) ÅCu Kα1 radiation, λ = 1.540560 Å
b = 5.53079 (13) ŵ = 0.56 mm1
c = 9.0323 (2) ÅT = 110 K
α = 79.0266 (10)°white
β = 75.7579 (9)°cylinder, ? × ? × ? mm
γ = 78.8261 (9)°
Data collection top
Inel CPS120
diffractometer
Scan method: Stationary detector
Specimen mounting: 0.7 mm diameter Lindemann capillary2θfixed = 0.15-105.83
Data collection mode: transmission
Refinement top
Rp = 0.0377046 data points
Rwp = 0.05074 parameters
Rexp = 0.01714 restraints
RBragg = 0.029
χ2 = 8.644
Crystal data top
C4H10Oγ = 78.8261 (9)°
Mr = 74.12V = 239.59 (1) Å3
Triclinic, P1Z = 2
a = 5.10141 (12) ÅCu Kα1 radiation, λ = 1.540560 Å
b = 5.53079 (13) ŵ = 0.56 mm1
c = 9.0323 (2) ÅT = 110 K
α = 79.0266 (10)°cylinder, ? × ? × ? mm
β = 75.7579 (9)°
Data collection top
Inel CPS120
diffractometer
Scan method: Stationary detector
Specimen mounting: 0.7 mm diameter Lindemann capillary2θfixed = 0.15-105.83
Data collection mode: transmission
Refinement top
Rp = 0.037χ2 = 8.644
Rwp = 0.0507046 data points
Rexp = 0.01774 parameters
RBragg = 0.02914 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1a0.5029 (9)0.3676 (9)0.8468 (5)0.0189 (12)*
C2a0.2385 (12)0.4899 (9)0.7975 (7)0.0189 (12)*
C3a0.2719 (9)0.7250 (8)0.6816 (5)0.0189 (15)*
C4a0.0165 (9)0.8354 (9)0.6231 (6)0.0189 (11)*
Oa0.4715 (6)0.1355 (5)0.9488 (4)0.0189 (8)*
H1a0.65160.33310.75450.025*
H1a'0.56370.48170.90080.025*
H2a0.17130.36750.75280.025*
H2a'0.09830.53340.89130.025*
H3a0.42610.68890.59210.025*
H3a'0.32080.85060.73250.025*
H4a0.04180.99330.54970.025*
H4a'0.03560.71780.56770.025*
H4a"0.14020.87460.71080.025*
HOa0.33660.07860.93610.025*
C1b0.9894 (9)0.7666 (9)0.1639 (6)0.0189 (13)*
C2b0.7372 (11)0.6333 (9)0.2104 (6)0.0189 (14)*
C3b0.7763 (9)0.4048 (7)0.3304 (5)0.0189 (15)*
C4b0.5293 (9)0.2656 (7)0.3640 (5)0.0189 (12)*
Ob0.9668 (6)0.9717 (5)0.0356 (3)0.0189 (8)*
H1b1.15850.64590.13210.025*
H1b'1.01090.83560.25410.025*
H2b0.70630.58110.11670.025*
H2b'0.57350.75240.25210.025*
H3b0.94800.29410.28910.025*
H3b'0.79430.45660.42720.025*
H4b0.55250.11120.44070.025*
H4b'0.50640.21710.26730.025*
H4b"0.35600.37270.40710.025*
HOb0.79991.03730.04340.025*
Geometric parameters (Å, º) top
C1a—C2a1.518 (8)C1b—C2b1.536 (7)
C1a—Oa1.442 (6)C1b—Ob1.469 (5)
C1a—H1a1.000C1b—H1b1.000
C1a—H1a'1.000C1b—H1b'1.000
C2a—C3a1.515 (6)C2b—C3b1.516 (6)
C2a—H2a1.000C2b—H2b1.000
C2a—H2a'1.000C2b—H2b'1.000
C3a—C4a1.503 (7)C3b—C4b1.540 (7)
C3a—H3a1.000C3b—H3b1.000
C3a—H3a'1.000C3b—H3b'1.000
C4a—H4a1.000C4b—H4b1.000
C4a—H4a'1.000C4b—H4b'1.000
C4a—H4a"1.000C4b—H4b"1.000
Oa—HOa0.850Ob—HOb0.850
C2a—C1a—Oa111.7 (4)C2b—C1b—Ob111.7 (4)
C2a—C1a—H1a110.4C2b—C1b—H1b110.1
C2a—C1a—H1a'110.0C2b—C1b—H1b'109.8
Oa—C1a—H1a108.3Ob—C1b—H1b108.7
Oa—C1a—H1a'108.8Ob—C1b—H1b'108.7
H1a—C1a—H1a'107.5H1b—C1b—H1b'107.7
C1a—C2a—C3a112.5 (4)C1b—C2b—C3b111.2 (4)
C1a—C2a—H2a109.0C1b—C2b—H2b109.1
C1a—C2a—H2a'108.4C1b—C2b—H2b'108.9
C3a—C2a—H2a110.0C3b—C2b—H2b109.1
C3a—C2a—H2a'108.7C3b—C2b—H2b'110.0
H2a—C2a—H2a'108.0H2b—C2b—H2b'108.5
C2a—C3a—C4a112.6 (4)C2b—C3b—C4b109.4 (4)
C2a—C3a—H3a109.9C2b—C3b—H3b108.7
C2a—C3a—H3a'108.5C2b—C3b—H3b'109.6
C4a—C3a—H3a109.2C4b—C3b—H3b110.0
C4a—C3a—H3a'108.9C4b—C3b—H3b'110.5
H3a—C3a—H3a'107.7H3b—C3b—H3b'109.0
C3a—C4a—H4a111.1C3b—C4b—H4b111.0
C3a—C4a—H4a'111.4C3b—C4b—H4b'110.8
C3a—C4a—H4a"110.5C3b—C4b—H4b"111.1
H4a—C4a—H4a'107.8H4b—C4b—H4b'108.4
H4a—C4a—H4a"108.0H4b—C4b—H4b"107.8
H4a'—C4a—H4a"107.9H4b'—C4b—H4b"107.7
C1a—Oa—HOa109.6C1b—Ob—HOb109.1
Oa—C1a—C2a—C3a176.1 (4)Ob—C1b—C2b—C3b173.7 (4)
C1a—C2a—C3a—C4a175.5 (4)C1b—C2b—C3b—C4b175.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2a—H2a···Obi1.0002.8583.596 (6)131.2
Oa—HOa···Obii0.8502.0282.776 (4)146.3
Ob—HOb···Oaiii0.8502.0022.764 (4)148.7
Symmetry codes: (i) x1, y, z+1; (ii) x1, y1, z+1; (iii) x, y+1, z1.

Experimental details

Crystal data
Chemical formulaC4H10O
Mr74.12
Crystal system, space groupTriclinic, P1
Temperature (K)110
a, b, c (Å)5.10141 (12), 5.53079 (13), 9.0323 (2)
α, β, γ (°)79.0266 (10), 75.7579 (9), 78.8261 (9)
V3)239.59 (1)
Z2
Radiation typeCu Kα1, λ = 1.540560 Å
µ (mm1)0.56
Specimen shape, size (mm)Cylinder, ? × ? × ?
Data collection
DiffractometerInel CPS120
diffractometer
Specimen mounting0.7 mm diameter Lindemann capillary
Data collection modeTransmission
Scan methodStationary detector
2θ values (°)2θfixed = 0.15-105.83
Refinement
R factors and goodness of fitRp = 0.037, Rwp = 0.050, Rexp = 0.017, RBragg = 0.029, χ2 = 8.644
No. of data points7046
No. of parameters74
No. of restraints14

Computer programs: SYMPHONIX, FOX, FULLPROF, ORTEP-3, SHELX97 and PARST.

Selected geometric parameters (Å, º) top
C1a—C2a1.518 (8)C1b—C2b1.536 (7)
C1a—Oa1.442 (6)C1b—Ob1.469 (5)
C2a—C3a1.515 (6)C2b—C3b1.516 (6)
C3a—C4a1.503 (7)C3b—C4b1.540 (7)
C2a—C1a—Oa111.7 (4)C2b—C1b—Ob111.7 (4)
C1a—C2a—C3a112.5 (4)C1b—C2b—C3b111.2 (4)
C2a—C3a—C4a112.6 (4)C2b—C3b—C4b109.4 (4)
Oa—C1a—C2a—C3a176.1 (4)Ob—C1b—C2b—C3b173.7 (4)
C1a—C2a—C3a—C4a175.5 (4)C1b—C2b—C3b—C4b175.5 (4)
 

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