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
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.
Crystal data top
C4H10O | V = 239.59 (1) Å3 |
Mr = 74.12 | Z = 2 |
Triclinic, P1 | F(000) = 84.0 |
Hall symbol: P 1 | Dx = 1.027 Mg m−3 |
a = 5.10141 (12) Å | Cu Kα1 radiation, λ = 1.540560 Å |
b = 5.53079 (13) Å | µ = 0.56 mm−1 |
c = 9.0323 (2) Å | T = 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 capillary | 2θfixed = 0.15-105.83 |
Data collection mode: transmission | |
Refinement top
Rp = 0.037 | 7046 data points |
Rwp = 0.050 | 74 parameters |
Rexp = 0.017 | 14 restraints |
RBragg = 0.029 | |
χ2 = 8.644 | |
Crystal data top
C4H10O | γ = 78.8261 (9)° |
Mr = 74.12 | V = 239.59 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.10141 (12) Å | Cu Kα1 radiation, λ = 1.540560 Å |
b = 5.53079 (13) Å | µ = 0.56 mm−1 |
c = 9.0323 (2) Å | T = 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 capillary | 2θfixed = 0.15-105.83 |
Data collection mode: transmission | |
Refinement top
Rp = 0.037 | χ2 = 8.644 |
Rwp = 0.050 | 7046 data points |
Rexp = 0.017 | 74 parameters |
RBragg = 0.029 | 14 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1a | 0.5029 (9) | 0.3676 (9) | 0.8468 (5) | 0.0189 (12)* | |
C2a | 0.2385 (12) | 0.4899 (9) | 0.7975 (7) | 0.0189 (12)* | |
C3a | 0.2719 (9) | 0.7250 (8) | 0.6816 (5) | 0.0189 (15)* | |
C4a | 0.0165 (9) | 0.8354 (9) | 0.6231 (6) | 0.0189 (11)* | |
Oa | 0.4715 (6) | 0.1355 (5) | 0.9488 (4) | 0.0189 (8)* | |
H1a | 0.6516 | 0.3331 | 0.7545 | 0.025* | |
H1a' | 0.5637 | 0.4817 | 0.9008 | 0.025* | |
H2a | 0.1713 | 0.3675 | 0.7528 | 0.025* | |
H2a' | 0.0983 | 0.5334 | 0.8913 | 0.025* | |
H3a | 0.4261 | 0.6889 | 0.5921 | 0.025* | |
H3a' | 0.3208 | 0.8506 | 0.7325 | 0.025* | |
H4a | 0.0418 | 0.9933 | 0.5497 | 0.025* | |
H4a' | −0.0356 | 0.7178 | 0.5677 | 0.025* | |
H4a" | −0.1402 | 0.8746 | 0.7108 | 0.025* | |
HOa | 0.3366 | 0.0786 | 0.9361 | 0.025* | |
C1b | 0.9894 (9) | 0.7666 (9) | 0.1639 (6) | 0.0189 (13)* | |
C2b | 0.7372 (11) | 0.6333 (9) | 0.2104 (6) | 0.0189 (14)* | |
C3b | 0.7763 (9) | 0.4048 (7) | 0.3304 (5) | 0.0189 (15)* | |
C4b | 0.5293 (9) | 0.2656 (7) | 0.3640 (5) | 0.0189 (12)* | |
Ob | 0.9668 (6) | 0.9717 (5) | 0.0356 (3) | 0.0189 (8)* | |
H1b | 1.1585 | 0.6459 | 0.1321 | 0.025* | |
H1b' | 1.0109 | 0.8356 | 0.2541 | 0.025* | |
H2b | 0.7063 | 0.5811 | 0.1167 | 0.025* | |
H2b' | 0.5735 | 0.7524 | 0.2521 | 0.025* | |
H3b | 0.9480 | 0.2941 | 0.2891 | 0.025* | |
H3b' | 0.7943 | 0.4566 | 0.4272 | 0.025* | |
H4b | 0.5525 | 0.1112 | 0.4407 | 0.025* | |
H4b' | 0.5064 | 0.2171 | 0.2673 | 0.025* | |
H4b" | 0.3560 | 0.3727 | 0.4071 | 0.025* | |
HOb | 0.7999 | 1.0373 | 0.0434 | 0.025* | |
Geometric parameters (Å, º) top
C1a—C2a | 1.518 (8) | C1b—C2b | 1.536 (7) |
C1a—Oa | 1.442 (6) | C1b—Ob | 1.469 (5) |
C1a—H1a | 1.000 | C1b—H1b | 1.000 |
C1a—H1a' | 1.000 | C1b—H1b' | 1.000 |
C2a—C3a | 1.515 (6) | C2b—C3b | 1.516 (6) |
C2a—H2a | 1.000 | C2b—H2b | 1.000 |
C2a—H2a' | 1.000 | C2b—H2b' | 1.000 |
C3a—C4a | 1.503 (7) | C3b—C4b | 1.540 (7) |
C3a—H3a | 1.000 | C3b—H3b | 1.000 |
C3a—H3a' | 1.000 | C3b—H3b' | 1.000 |
C4a—H4a | 1.000 | C4b—H4b | 1.000 |
C4a—H4a' | 1.000 | C4b—H4b' | 1.000 |
C4a—H4a" | 1.000 | C4b—H4b" | 1.000 |
Oa—HOa | 0.850 | Ob—HOb | 0.850 |
| | | |
C2a—C1a—Oa | 111.7 (4) | C2b—C1b—Ob | 111.7 (4) |
C2a—C1a—H1a | 110.4 | C2b—C1b—H1b | 110.1 |
C2a—C1a—H1a' | 110.0 | C2b—C1b—H1b' | 109.8 |
Oa—C1a—H1a | 108.3 | Ob—C1b—H1b | 108.7 |
Oa—C1a—H1a' | 108.8 | Ob—C1b—H1b' | 108.7 |
H1a—C1a—H1a' | 107.5 | H1b—C1b—H1b' | 107.7 |
C1a—C2a—C3a | 112.5 (4) | C1b—C2b—C3b | 111.2 (4) |
C1a—C2a—H2a | 109.0 | C1b—C2b—H2b | 109.1 |
C1a—C2a—H2a' | 108.4 | C1b—C2b—H2b' | 108.9 |
C3a—C2a—H2a | 110.0 | C3b—C2b—H2b | 109.1 |
C3a—C2a—H2a' | 108.7 | C3b—C2b—H2b' | 110.0 |
H2a—C2a—H2a' | 108.0 | H2b—C2b—H2b' | 108.5 |
C2a—C3a—C4a | 112.6 (4) | C2b—C3b—C4b | 109.4 (4) |
C2a—C3a—H3a | 109.9 | C2b—C3b—H3b | 108.7 |
C2a—C3a—H3a' | 108.5 | C2b—C3b—H3b' | 109.6 |
C4a—C3a—H3a | 109.2 | C4b—C3b—H3b | 110.0 |
C4a—C3a—H3a' | 108.9 | C4b—C3b—H3b' | 110.5 |
H3a—C3a—H3a' | 107.7 | H3b—C3b—H3b' | 109.0 |
C3a—C4a—H4a | 111.1 | C3b—C4b—H4b | 111.0 |
C3a—C4a—H4a' | 111.4 | C3b—C4b—H4b' | 110.8 |
C3a—C4a—H4a" | 110.5 | C3b—C4b—H4b" | 111.1 |
H4a—C4a—H4a' | 107.8 | H4b—C4b—H4b' | 108.4 |
H4a—C4a—H4a" | 108.0 | H4b—C4b—H4b" | 107.8 |
H4a'—C4a—H4a" | 107.9 | H4b'—C4b—H4b" | 107.7 |
C1a—Oa—HOa | 109.6 | C1b—Ob—HOb | 109.1 |
| | | |
Oa—C1a—C2a—C3a | −176.1 (4) | Ob—C1b—C2b—C3b | 173.7 (4) |
C1a—C2a—C3a—C4a | 175.5 (4) | C1b—C2b—C3b—C4b | −175.5 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2a—H2a′···Obi | 1.000 | 2.858 | 3.596 (6) | 131.2 |
Oa—HOa···Obii | 0.850 | 2.028 | 2.776 (4) | 146.3 |
Ob—HOb···Oaiii | 0.850 | 2.002 | 2.764 (4) | 148.7 |
Symmetry codes: (i) x−1, y, z+1; (ii) x−1, y−1, z+1; (iii) x, y+1, z−1. |
Experimental details
Crystal data |
Chemical formula | C4H10O |
Mr | 74.12 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 239.59 (1) |
Z | 2 |
Radiation type | Cu Kα1, λ = 1.540560 Å |
µ (mm−1) | 0.56 |
Specimen shape, size (mm) | Cylinder, ? × ? × ? |
|
Data collection |
Diffractometer | Inel CPS120 diffractometer |
Specimen mounting | 0.7 mm diameter Lindemann capillary |
Data collection mode | Transmission |
Scan method | Stationary detector |
2θ values (°) | 2θfixed = 0.15-105.83 |
|
Refinement |
R factors and goodness of fit | Rp = 0.037, Rwp = 0.050, Rexp = 0.017, RBragg = 0.029, χ2 = 8.644 |
No. of data points | 7046 |
No. of parameters | 74 |
No. of restraints | 14 |
Selected geometric parameters (Å, º) topC1a—C2a | 1.518 (8) | C1b—C2b | 1.536 (7) |
C1a—Oa | 1.442 (6) | C1b—Ob | 1.469 (5) |
C2a—C3a | 1.515 (6) | C2b—C3b | 1.516 (6) |
C3a—C4a | 1.503 (7) | C3b—C4b | 1.540 (7) |
| | | |
C2a—C1a—Oa | 111.7 (4) | C2b—C1b—Ob | 111.7 (4) |
C1a—C2a—C3a | 112.5 (4) | C1b—C2b—C3b | 111.2 (4) |
C2a—C3a—C4a | 112.6 (4) | C2b—C3b—C4b | 109.4 (4) |
| | | |
Oa—C1a—C2a—C3a | −176.1 (4) | Ob—C1b—C2b—C3b | 173.7 (4) |
C1a—C2a—C3a—C4a | 175.5 (4) | C1b—C2b—C3b—C4b | −175.5 (4) |