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The crystal structure of the solid phase of the dipolar aprotic solvent γ-butyrolactone (BL1), C4H6O2, has been solved using the atom–atom potential method and Rietveld-refined against powder diffraction data collected at T = 180 K with a curved position-sensitive detector (INEL CPS120) using Debye–Scherrer diffraction geometry with monochromatic X-rays. It was first deduced from the X-ray experiment that the lattice parameters are a = 10.1282 (4), b = 10.2303 (5), c = 8.3133 (4) Å, β = 93.291 (2)° and that the space group is P21/a, with Z = 8 and two independent molecules in the asymmetric unit. The structure was then solved by global energy minimization of the crystal-lattice atom–atom potentials. The subsequent GSAS-based Rietveld refinement converged to the final crystal-structure model indicator RF2 = 0.0684, profile factors Rp = 0.0517 and Rwp = 0.0694, and a reduced χ2 = 1.671. After further cycles of heating and cooling, a powder diffraction pattern markedly different from the first pattern was obtained, again at T = 180 K, which we tentatively assign to a second polymorph (BL2). All the observed diffraction peaks are well indexed by a triclinic unit cell essentially featuring a doubling of the a axis. An excellent Le Bail fit is obtained, for which Rp = 0.0312 and Rwp = 0.0511.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105005392/lc5018sup1.cif
Contains datablock BL180_publ

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105005392/lc5018sup2.cif
Contains datablock BL180_publ

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105005392/lc5018sup3.cif
Contains datablock BL180_publ

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768105005392/lc5018sup4.cif
Contains datablock BL2_180_publ

txt

Text file https://doi.org/10.1107/S0108768105005392/lc5018sup5.txt
BL1 data at T = 180 K

txt

Text file https://doi.org/10.1107/S0108768105005392/lc5018sup6.txt
BL2 data at T = 180 K

txt

Text file https://doi.org/10.1107/S0108768105005392/lc5018sup7.txt
BL1 Fullprof data

txt

Text file https://doi.org/10.1107/S0108768105005392/lc5018sup8.txt
BL2 Fullprof data

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108768105005392/lc5018sup9.pdf
XRD Spectum

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108768105005392/lc5018sup10.pdf
XRD spectra

CCDC reference: 1159011

Computing details top

Program(s) used to refine structure: GSAS.

4-Hydroxybutyric acid gamma-Lactone top
Crystal data top
C4H6O2V = 859.95 (7) Å3
Mr = 86.08Z = 8
Monoclinic, P21/aDx = 1.33 Mg m3
Hall symbol: -P 2yabCu Kα1 radiation, λ = 1.54056 Å
a = 10.1282 (4) ÅT = 180 K
b = 10.2303 (5) Åwhite
c = 8.3133 (4) Å?, ? × ? × ? mm
β = 93.2908 (17)°Specimen preparation: Prepared at cooled down from 300 to 180 K and 1atm kPa, cooled at 6 K min1
Data collection top
INEL CPS 120
diffractometer
2θmin = 0.302°, 2θmax = 114.533°, 2θstep = 0.029°
Radiation source: sealed X-ray tube, INEL CPS 120
Refinement top
Least-squares matrix: fullProfile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in P. Thompson, D.E. Cox & J.B. Hastings (1987). J. Appl. Cryst.,20,79-83. Asymmetry correction of L.W. Finger, D.E. Cox & A. P. Jephcoat (1994). J. Appl. Cryst.,27,892-900. Microstrain broadening by P.W. Stephens, (1999). J. Appl. Cryst.,32,281-289. #1(GU) = 220.927 #2(GV) = -88.488 #3(GW) = 20.788 #4(GP) = 0.000 #5(LX) = 1.657 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0000 #11(H/L) = 0.0000 #12(eta) = 0.0000 #13(S400 ) = 0.0E+00 #14(S040 ) = 0.0E+00 #15(S004 ) = 0.0E+00 #16(S220 ) = 0.0E+00 #17(S202 ) = 0.0E+00 #18(S022 ) = 0.0E+00 #19(S301 ) = 0.0E+00 #20(S103 ) = 0.0E+00 #21(S121 ) = 0.0E+00 Peak tails are ignored where the intensity is below 0.0001 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rp = 0.052115 parameters
Rwp = 0.06958 restraints
Rexp = 0.060(Δ/σ)max = 0.01
R(F2) = 0.06663Background function: GSAS Background function number 1 with 6 terms. Shifted Chebyshev function of 1st kind 1: -2.45382 2: 1.36696 3: -0.793512 4: 0.878383 5: 2.31191 6: 1.70787
χ2 = 1.664Preferred orientation correction: Spherical Harmonic ODF Spherical harmonic order= 10 The sample symmetry is: cylindrical (fiber texture) Index = 2 0 -2 Coeff= -0.1928 Index = 2 0 0 Coeff= 0.4183 Index = 2 0 2 Coeff= 0.0753 Index = 4 0 -4 Coeff= 0.1166 Index = 4 0 -2 Coeff= 1.1450 Index = 4 0 0 Coeff= 0.2432 Index = 4 0 2 Coeff= 0.7345 Index = 4 0 4 Coeff= 0.6219 Index = 6 0 -6 Coeff= -1.9053 Index = 6 0 -4 Coeff= 1.2835 Index = 6 0 -2 Coeff= -0.3569 Index = 6 0 0 Coeff= -2.1792 Index = 6 0 2 Coeff= 0.2381 Index = 6 0 4 Coeff= 2.4571 Index = 6 0 6 Coeff= 0.9538 Index = 8 0 -8 Coeff= 0.9905 Index = 8 0 -6 Coeff= -0.0950 Index = 8 0 -4 Coeff= 1.6723 Index = 8 0 -2 Coeff= -1.9020 Index = 8 0 0 Coeff= 3.0183 Index = 8 0 2 Coeff= -0.7880 Index = 8 0 4 Coeff= 1.3471 Index = 8 0 6 Coeff= -1.1220 Index = 8 0 8 Coeff= 1.8006 Index = 10 0-10 Coeff= -0.5927 Index = 10 0 -8 Coeff= 1.0910 Index = 10 0 -6 Coeff= -0.3130 Index = 10 0 -4 Coeff= 1.6547 Index = 10 0 -2 Coeff= -1.0295 Index = 10 0 0 Coeff= 2.0994 Index = 10 0 2 Coeff= 0.2394 Index = 10 0 4 Coeff= -0.3914 Index = 10 0 6 Coeff= 0.3136 Index = 10 0 8 Coeff= 1.0738 Index = 10 0 10 Coeff= -0.8861 Prefered orientation correction range: Min= -0.40080, Max= 3.82007
3940 data points
Crystal data top
C4H6O2β = 93.2908 (17)°
Mr = 86.08V = 859.95 (7) Å3
Monoclinic, P21/aZ = 8
a = 10.1282 (4) ÅCu Kα1 radiation, λ = 1.54056 Å
b = 10.2303 (5) ÅT = 180 K
c = 8.3133 (4) Å?, ? × ? × ? mm
Data collection top
INEL CPS 120
diffractometer
2θmin = 0.302°, 2θmax = 114.533°, 2θstep = 0.029°
Refinement top
Rp = 0.052χ2 = 1.664
Rwp = 0.0693940 data points
Rexp = 0.060115 parameters
R(F2) = 0.0666358 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1a0.066 (4)0.047 (3)0.218 (3)0.029 (19)*
O2a0.018 (3)0.165 (2)0.172 (5)0.029 (19)*
C1a0.042 (3)0.274 (4)0.064 (5)0.029 (19)*
C2a0.193 (3)0.253 (4)0.037 (5)0.029 (19)*
C3a0.217 (2)0.109 (4)0.074 (4)0.029 (19)*
C4a0.084 (2)0.052 (3)0.139 (2)0.029 (19)*
O1b0.023 (3)0.421 (4)0.282 (4)0.029 (19)*
O2b0.173 (4)0.504 (2)0.349 (5)0.029 (19)*
C1b0.283 (6)0.486 (2)0.450 (6)0.029 (19)*
C2b0.284 (3)0.335 (3)0.458 (5)0.029 (19)*
C3b0.152 (4)0.290 (2)0.399 (5)0.029 (19)*
C4b0.075 (4)0.413 (2)0.359 (3)0.029 (19)*
H1a0.026 (5)0.369 (3)0.114 (10)0.029 (19)*
H2a0.001 (6)0.266 (8)0.051 (7)0.029 (19)*
H3a0.222 (8)0.273 (7)0.086 (8)0.029 (19)*
H4a0.243 (4)0.314 (4)0.118 (12)0.029 (19)*
H5a0.288 (4)0.101 (5)0.164 (8)0.029 (19)*
H6a0.250 (4)0.058 (5)0.034 (7)0.029 (19)*
H1b0.377 (6)0.518 (6)0.400 (15)0.029 (19)*
H2b0.268 (13)0.522 (7)0.572 (8)0.029 (19)*
H3b0.294 (9)0.305 (7)0.580 (8)0.029 (19)*
H4b0.364 (4)0.300 (5)0.380 (14)0.029 (19)*
H5b0.168 (8)0.232 (6)0.293 (10)0.029 (19)*
H6b0.098 (4)0.236 (7)0.492 (11)0.029 (19)*
Geometric parameters (Å, º) top
O1a—C4a1.2099 (8)C3b—C2b1.5293 (8)
O2a—C1a1.4398 (8)C3b—C4b1.5298 (8)
O2a—C3a2.20 (4)C3b—H5b1.072 (4)
O2a—C4a1.3600 (8)C3b—H6b1.072 (4)
C1a—O2a1.4398 (8)C4b—O1b1.2099 (8)
C1a—C2a1.5495 (8)C4b—O2b1.3600 (8)
C1a—H1a1.073 (4)C4b—C3b1.5298 (8)
C1a—H2a1.073 (4)H1a—C1a1.073 (4)
C2a—C1a1.5495 (8)H1a—H2a1.764 (8)
C2a—C3a1.5294 (8)H2a—C1a1.073 (4)
C2a—H3a1.068 (4)H2a—H1a1.764 (8)
C2a—H4a1.068 (4)H3a—C2a1.068 (4)
C3a—O2a2.20 (4)H3a—H4a1.774 (8)
C3a—C2a1.5294 (8)H4a—C2a1.068 (4)
C3a—C4a1.5297 (8)H4a—H3a1.774 (8)
C3a—H5a1.072 (4)H5a—C3a1.072 (4)
C3a—H6a1.072 (4)H5a—H6a1.766 (8)
C4a—O1a1.2099 (8)H6a—C3a1.072 (4)
C4a—O2a1.3600 (8)H6a—H5a1.766 (8)
C4a—C3a1.5297 (8)H1b—C1b1.075 (4)
O1b—C4b1.2099 (8)H1b—H2b1.760 (8)
O2b—C1b1.4399 (8)H2b—C1b1.075 (4)
O2b—C4b1.3600 (8)H2b—H1b1.760 (8)
C1b—O2b1.4399 (8)H3b—C2b1.068 (4)
C1b—C2b1.5495 (8)H3b—H4b1.774 (8)
C1b—H1b1.075 (4)H4b—C2b1.068 (4)
C1b—H2b1.075 (4)H4b—H3b1.774 (8)
C2b—C1b1.5495 (8)H5b—C3b1.072 (4)
C2b—C3b1.5293 (8)H5b—H6b1.767 (8)
C2b—H3b1.068 (4)H6b—C3b1.072 (4)
C2b—H4b1.068 (4)H6b—H5b1.767 (8)
C1a—O2a—C4a118 (2)C1b—O2b—C4b118 (3)
O2a—C1a—C2a96.5 (19)O2b—C1b—C2b99.2 (17)
O2a—C1a—H1a116.2 (7)O2b—C1b—H1b115.8 (7)
O2a—C1a—H2a116.2 (7)O2b—C1b—H2b115.7 (7)
C2a—C1a—H1a108.0 (7)C2b—C1b—H1b107.6 (6)
C2a—C1a—H2a107.9 (7)C2b—C1b—H2b107.6 (6)
H1a—C1a—H2a110.6 (8)H1b—C1b—H2b109.8 (8)
C1a—C2a—C3a105.5 (15)C1b—C2b—C3b105.9 (14)
C1a—C2a—H3a109.0 (6)C1b—C2b—H3b108.9 (6)
C1a—C2a—H4a109.0 (7)C1b—C2b—H4b108.9 (6)
C3a—C2a—H3a110.5 (7)C3b—C2b—H3b110.3 (7)
C3a—C2a—H4a110.4 (7)C3b—C2b—H4b110.3 (7)
H3a—C2a—H4a112.3 (8)H3b—C2b—H4b112.2 (8)
C2a—C3a—C4a107.1 (15)C2b—C3b—C4b106.8 (15)
C2a—C3a—H5a109.7 (7)C2b—C3b—H5b109.7 (7)
C2a—C3a—H6a109.7 (7)C2b—C3b—H6b109.7 (7)
C4a—C3a—H5a109.7 (7)C4b—C3b—H5b109.7 (7)
C4a—C3a—H6a109.6 (7)C4b—C3b—H6b109.7 (7)
H5a—C3a—H6a110.9 (8)H5b—C3b—H6b111.1 (8)
O1a—C4a—O2a123.04 (18)O1b—C4b—O2b123.04 (18)
O1a—C4a—C3a127.39 (19)O1b—C4b—C3b127.39 (19)
O2a—C4a—C3a99 (3)O2b—C4b—C3b101 (3)

Experimental details

Crystal data
Chemical formulaC4H6O2
Mr86.08
Crystal system, space groupMonoclinic, P21/a
Temperature (K)180
a, b, c (Å)10.1282 (4), 10.2303 (5), 8.3133 (4)
β (°) 93.2908 (17)
V3)859.95 (7)
Z8
Radiation typeCu Kα1, λ = 1.54056 Å
Specimen shape, size (mm)?, ? × ? × ?
Data collection
DiffractometerINEL CPS 120
diffractometer
Specimen mounting?
Data collection mode?
Scan method?
2θ values (°)2θmin = 0.302 2θmax = 114.533 2θstep = 0.029
Refinement
R factors and goodness of fitRp = 0.052, Rwp = 0.069, Rexp = 0.060, R(F2) = 0.06663, χ2 = 1.664
No. of data points3940
No. of parameters115
No. of restraints58

Computer programs: GSAS.

 

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