Growth and characterization of large centimetre-size levoglucosan single crystals

Levoglucosan is a typical orientationally disordered crystalline material (the molecules are long-range positionally ordered but orientationally disordered). At present, experimental research on its glass transition is mainly focused on polycrystals, while the study of the corresponding single crystals is rarely reported. Centimetre-size (maximum dimensions of 2.1 × 0.9 × 0.4 cm) levoglucosan single crystals of high quality were grown by the solution method, laying a necessary foundation for experimental measurements of the glass transition mechanism in the material.

Computing details

Cell refinement: SAINT V8.38A (?, 2016) for 298K; SAINT v8.34A (Bruker, 2013) for 248K, 198K. Data reduction: SAINT V8.38A (?, 2016) for 298K; SAINT v8.34A (Bruker, 2013) for 248K, 198K. For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(298K)

Crystal data

C6H10O5	F(000) = 344
Mr = 162.14	Dx = 1.613 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 6.676 (4) Å	Cell parameters from 865 reflections
b = 7.531 (4) Å	θ = 3.1–22.2°
c = 13.279 (7) Å	µ = 0.14 mm^−1
V = 667.6 (6) Å^3	T = 296 K
Z = 4	Block

Data collection

CCD area detector diffractometer	Rint = 0.038
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
phi and ω scans	h = −8→8
4172 measured reflections	k = −9→9
1522 independent reflections	l = −13→17
1209 reflections with I > 2σ(I)

Refinement

Refinement on F^2	All H-atom parameters refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0456P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.038	(Δ/σ)max < 0.001
wR(F^2) = 0.095	Δρmax = 0.19 e Å^−3
S = 1.05	Δρmin = −0.19 e Å^−3
1522 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
141 parameters	Extinction coefficient: 0.042 (8)
0 restraints	Absolute structure: Flack x determined using 387 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Hydrogen site location: difference Fourier map	Absolute structure parameter: −0.1 (10)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8220 (4)	0.1231 (4)	0.9461 (2)	0.0225 (6)
C2	1.0052 (4)	0.0742 (4)	0.8809 (2)	0.0230 (7)
C3	0.6656 (5)	−0.1488 (4)	0.8668 (2)	0.0279 (7)
C4	0.6770 (5)	−0.0332 (4)	0.9604 (2)	0.0244 (7)
C5	0.9490 (5)	−0.0555 (5)	0.7982 (2)	0.0291 (8)
C6	0.6074 (6)	−0.0463 (6)	0.7732 (3)	0.0342 (8)
O1	0.7444 (4)	−0.1462 (3)	1.04034 (18)	0.0307 (6)
O2	1.1640 (3)	0.0032 (3)	0.94013 (17)	0.0303 (5)
O3	0.7977 (3)	0.0170 (3)	0.73476 (15)	0.0362 (6)
O4	0.7233 (4)	0.2687 (3)	0.89911 (17)	0.0343 (6)
O5	0.8650 (3)	−0.2092 (3)	0.84086 (15)	0.0298 (6)
H3	0.583 (4)	−0.254 (3)	0.880 (2)	0.014 (7)*
H4	0.543 (5)	0.019 (4)	0.9734 (19)	0.013 (7)*
H2	1.060 (5)	0.191 (4)	0.854 (2)	0.026 (8)*
H5	1.068 (5)	−0.089 (5)	0.759 (3)	0.035 (10)*
H1	0.858 (4)	0.158 (4)	1.010 (2)	0.019 (7)*
H6A	0.549 (5)	−0.120 (5)	0.726 (3)	0.035 (10)*
H4A	0.713 (6)	0.347 (5)	0.940 (3)	0.040 (11)*
H1A	0.733 (8)	−0.099 (6)	1.089 (4)	0.070 (15)*
H2A	1.149 (7)	−0.103 (6)	0.948 (3)	0.075 (16)*
H6B	0.530 (6)	0.056 (6)	0.789 (3)	0.046 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0245 (16)	0.0238 (13)	0.0192 (15)	0.0041 (13)	−0.0012 (12)	−0.0015 (12)
C2	0.0219 (15)	0.0247 (15)	0.0224 (15)	−0.0001 (12)	0.0011 (12)	0.0007 (12)
C3	0.0291 (17)	0.0321 (15)	0.0225 (16)	−0.0072 (14)	−0.0036 (14)	−0.0005 (13)
C4	0.0242 (16)	0.0295 (15)	0.0196 (14)	−0.0002 (13)	0.0011 (12)	−0.0008 (12)
C5	0.0304 (18)	0.0368 (19)	0.0200 (15)	−0.0027 (15)	0.0032 (14)	−0.0032 (14)
C6	0.035 (2)	0.043 (2)	0.0246 (17)	−0.0064 (18)	−0.0094 (15)	0.0008 (16)
O1	0.0412 (14)	0.0312 (11)	0.0197 (12)	−0.0016 (11)	0.0031 (11)	0.0026 (10)
O2	0.0266 (12)	0.0265 (11)	0.0379 (12)	0.0017 (10)	−0.0041 (9)	−0.0032 (10)
O3	0.0384 (15)	0.0502 (14)	0.0199 (11)	−0.0076 (11)	−0.0030 (10)	0.0068 (11)
O4	0.0438 (14)	0.0259 (11)	0.0332 (13)	0.0112 (10)	−0.0052 (11)	−0.0001 (10)
O5	0.0351 (12)	0.0265 (10)	0.0277 (12)	−0.0002 (10)	0.0023 (10)	−0.0059 (10)

Geometric parameters (Å, º)

C1—C2	1.543 (4)	C3—C6	1.514 (4)
C1—C4	1.536 (4)	C3—O5	1.448 (4)
C1—O4	1.424 (3)	C4—O1	1.433 (4)
C2—C5	1.517 (4)	C5—O3	1.424 (4)
C2—O2	1.424 (4)	C5—O5	1.406 (4)
C3—C4	1.519 (4)	C6—O3	1.449 (4)
C4—C1—C2	112.7 (2)	C3—C4—C1	111.7 (2)
O4—C1—C2	107.8 (2)	O1—C4—C1	110.4 (2)
O4—C1—C4	110.6 (2)	O1—C4—C3	106.3 (2)
C5—C2—C1	111.3 (3)	O3—C5—C2	110.9 (3)
O2—C2—C1	111.7 (2)	O5—C5—C2	109.7 (2)
O2—C2—C5	110.0 (2)	O5—C5—O3	105.7 (3)
C6—C3—C4	113.1 (3)	O3—C6—C3	103.4 (3)
O5—C3—C4	109.2 (2)	C5—O3—C6	106.7 (2)
O5—C3—C6	101.6 (3)	C5—O5—C3	101.8 (2)

(248K)

Crystal data

C6H10O5	F(000) = 344
Mr = 162.14	Dx = 1.626 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 6.6601 (17) Å	Cell parameters from 1456 reflections
b = 7.5006 (19) Å	θ = 3.1–24.4°
c = 13.260 (3) Å	µ = 0.14 mm^−1
V = 662.4 (3) Å^3	T = 246 K
Z = 4	Block

Data collection

CCD area detector diffractometer	Rint = 0.031
Graphite monochromator	θmax = 27.3°, θmin = 3.1°
phi and ω scans	h = −7→8
4080 measured reflections	k = −9→9
1498 independent reflections	l = −17→9
1323 reflections with I > 2σ(I)

Refinement

Refinement on F^2	All H-atom parameters refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 0.0643P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.031	(Δ/σ)max < 0.001
wR(F^2) = 0.068	Δρmax = 0.17 e Å^−3
S = 1.04	Δρmin = −0.15 e Å^−3
1498 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
141 parameters	Extinction coefficient: 0.085 (8)
0 restraints	Absolute structure: Flack x determined using 481 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Hydrogen site location: difference Fourier map	Absolute structure parameter: −0.1 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.8236 (3)	−0.1245 (3)	−0.94621 (16)	0.0183 (4)
C2	−1.0061 (3)	−0.0750 (3)	−0.88108 (16)	0.0197 (5)
C3	−0.6661 (3)	0.1487 (3)	−0.86725 (17)	0.0224 (5)
C4	−0.6773 (3)	0.0331 (3)	−0.96043 (16)	0.0198 (5)
C5	−0.9505 (4)	0.0556 (3)	−0.79837 (17)	0.0239 (5)
C6	−0.6076 (4)	0.0450 (4)	−0.77337 (19)	0.0286 (6)
O1	−0.7449 (3)	0.1455 (2)	−1.04075 (12)	0.0243 (4)
O2	−1.1656 (2)	−0.0029 (2)	−0.94007 (13)	0.0246 (4)
O3	−0.7980 (2)	−0.0177 (2)	−0.73485 (11)	0.0299 (4)
O4	−0.7238 (3)	−0.2705 (2)	−0.89885 (13)	0.0276 (4)
O5	−0.8652 (2)	0.20953 (19)	−0.84095 (12)	0.0245 (4)
H3	−0.587 (3)	0.255 (3)	−0.8789 (17)	0.014 (5)*
H4	−0.541 (3)	−0.016 (3)	−0.9731 (16)	0.015 (5)*
H2	−1.058 (4)	−0.191 (3)	−0.8509 (19)	0.028 (6)*
H5	−1.069 (3)	0.089 (3)	−0.759 (2)	0.027 (7)*
H1	−0.869 (3)	−0.161 (3)	−1.0137 (17)	0.016 (6)*
H6A	−0.544 (4)	0.119 (4)	−0.724 (2)	0.035 (8)*
H4A	−0.705 (4)	−0.352 (4)	−0.942 (2)	0.036 (7)*
H1A	−0.707 (5)	0.095 (4)	−1.094 (3)	0.058 (10)*
H2A	−1.159 (4)	0.103 (4)	−0.947 (2)	0.043 (9)*
H6B	−0.518 (4)	−0.057 (4)	−0.7901 (18)	0.029 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0220 (11)	0.0181 (9)	0.0148 (10)	0.0036 (9)	−0.0026 (9)	−0.0007 (8)
C2	0.0198 (10)	0.0198 (10)	0.0195 (11)	−0.0014 (8)	0.0006 (9)	0.0024 (9)
C3	0.0220 (11)	0.0250 (10)	0.0202 (11)	−0.0057 (9)	−0.0005 (10)	−0.0005 (9)
C4	0.0181 (11)	0.0236 (11)	0.0176 (10)	0.0012 (9)	0.0009 (9)	0.0007 (9)
C5	0.0251 (12)	0.0299 (13)	0.0168 (10)	−0.0022 (10)	0.0021 (10)	−0.0015 (10)
C6	0.0290 (13)	0.0354 (14)	0.0214 (12)	−0.0053 (11)	−0.0064 (11)	−0.0013 (11)
O1	0.0328 (9)	0.0247 (8)	0.0155 (8)	−0.0013 (7)	0.0026 (7)	0.0022 (7)
O2	0.0225 (8)	0.0202 (8)	0.0310 (9)	0.0012 (7)	−0.0062 (7)	−0.0012 (7)
O3	0.0326 (9)	0.0419 (10)	0.0151 (7)	−0.0074 (8)	−0.0026 (7)	0.0057 (7)
O4	0.0352 (9)	0.0215 (8)	0.0259 (9)	0.0091 (7)	−0.0035 (8)	−0.0013 (7)
O5	0.0288 (8)	0.0220 (7)	0.0225 (8)	0.0006 (7)	0.0014 (7)	−0.0046 (7)

Geometric parameters (Å, º)

C1—C2	1.537 (3)	C3—C6	1.519 (3)
C1—C4	1.543 (3)	C3—O5	1.445 (3)
C1—O4	1.427 (2)	C4—O1	1.431 (3)
C2—C5	1.517 (3)	C5—O3	1.430 (3)
C2—O2	1.425 (3)	C5—O5	1.405 (3)
C3—C4	1.511 (3)	C6—O3	1.445 (3)
C2—C1—C4	112.51 (17)	C3—C4—C1	111.76 (17)
O4—C1—C2	107.86 (17)	O1—C4—C1	110.11 (17)
O4—C1—C4	110.35 (16)	O1—C4—C3	106.64 (16)
C5—C2—C1	111.66 (18)	O3—C5—C2	110.6 (2)
O2—C2—C1	111.88 (17)	O5—C5—C2	109.80 (18)
O2—C2—C5	109.52 (18)	O5—C5—O3	105.40 (17)
C4—C3—C6	112.91 (19)	O3—C6—C3	103.40 (18)
O5—C3—C4	109.45 (17)	C5—O3—C6	106.84 (16)
O5—C3—C6	101.48 (18)	C5—O5—C3	102.05 (16)

(198K)

Crystal data

C6H10O5	F(000) = 344
Mr = 162.14	Dx = 1.635 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 6.6457 (18) Å	Cell parameters from 1460 reflections
b = 7.476 (2) Å	θ = 3.1–24.4°
c = 13.260 (4) Å	µ = 0.14 mm^−1
V = 658.9 (3) Å^3	T = 198 K
Z = 4	Block

Data collection

CCD area detector diffractometer	Rint = 0.035
Graphite monochromator	θmax = 27.2°, θmin = 3.1°
phi and ω scans	h = −7→8
3988 measured reflections	k = −9→9
1462 independent reflections	l = −17→9
1303 reflections with I > 2σ(I)

Refinement

Refinement on F^2	All H-atom parameters refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 0.003P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.032	(Δ/σ)max < 0.001
wR(F^2) = 0.075	Δρmax = 0.25 e Å^−3
S = 1.10	Δρmin = −0.19 e Å^−3
1462 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
141 parameters	Extinction coefficient: 0.149 (13)
0 restraints	Absolute structure: Flack x determined using 486 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Hydrogen site location: difference Fourier map	Absolute structure parameter: −0.2 (8)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8239 (3)	1.1255 (3)	0.94603 (17)	0.0151 (5)
C2	1.0075 (3)	1.0752 (3)	0.88107 (17)	0.0155 (5)
C3	0.6662 (3)	0.8514 (3)	0.86716 (18)	0.0181 (5)
C4	0.6778 (3)	0.9678 (3)	0.96059 (17)	0.0158 (5)
C5	0.9504 (4)	0.9444 (3)	0.79833 (18)	0.0193 (5)
C6	0.6071 (4)	0.9559 (4)	0.77347 (19)	0.0229 (6)
O1	0.7455 (3)	0.8550 (2)	1.04093 (13)	0.0196 (4)
O2	1.1669 (2)	1.0026 (2)	0.94016 (13)	0.0195 (4)
O3	0.7984 (2)	1.0181 (2)	0.73489 (12)	0.0235 (4)
O4	0.7246 (3)	1.2721 (2)	0.89861 (13)	0.0214 (4)
O5	0.8652 (2)	0.7903 (2)	0.84094 (12)	0.0192 (4)
H3	0.584 (3)	0.746 (3)	0.8775 (18)	0.009 (6)*
H4	0.543 (4)	1.020 (3)	0.9745 (17)	0.010 (6)*
H2	1.061 (4)	1.190 (3)	0.8504 (18)	0.014 (6)*
H5	1.068 (3)	0.910 (3)	0.761 (2)	0.018 (7)*
H1	0.870 (4)	1.159 (3)	1.0129 (19)	0.014 (6)*
H6A	0.543 (4)	0.876 (4)	0.728 (2)	0.027 (8)*
H4A	0.709 (4)	1.356 (4)	0.942 (2)	0.021 (7)*
H1A	0.711 (5)	0.901 (4)	1.090 (3)	0.047 (10)*
H2A	1.159 (5)	0.890 (5)	0.946 (3)	0.052 (10)*
H6B	0.523 (4)	1.057 (4)	0.7925 (19)	0.025 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0170 (11)	0.0139 (9)	0.0145 (11)	0.0027 (9)	−0.0017 (9)	−0.0004 (9)
C2	0.0141 (10)	0.0157 (11)	0.0166 (11)	−0.0008 (8)	0.0008 (9)	0.0009 (9)
C3	0.0176 (11)	0.0194 (10)	0.0174 (11)	−0.0056 (9)	−0.0017 (10)	0.0007 (9)
C4	0.0144 (11)	0.0187 (11)	0.0143 (10)	0.0012 (9)	0.0006 (9)	0.0011 (9)
C5	0.0193 (12)	0.0233 (12)	0.0153 (11)	0.0005 (10)	0.0015 (10)	0.0001 (10)
C6	0.0234 (13)	0.0279 (13)	0.0173 (12)	−0.0048 (11)	−0.0043 (10)	0.0000 (10)
O1	0.0257 (9)	0.0199 (8)	0.0132 (8)	−0.0015 (7)	0.0016 (7)	0.0019 (7)
O2	0.0178 (8)	0.0154 (8)	0.0254 (9)	0.0012 (7)	−0.0049 (7)	−0.0012 (7)
O3	0.0246 (9)	0.0331 (9)	0.0127 (8)	−0.0050 (7)	−0.0017 (7)	0.0047 (7)
O4	0.0283 (9)	0.0151 (8)	0.0209 (9)	0.0070 (7)	−0.0026 (7)	0.0008 (7)
O5	0.0222 (8)	0.0178 (7)	0.0174 (8)	0.0005 (7)	0.0017 (7)	−0.0029 (7)

Geometric parameters (Å, º)

C1—C2	1.541 (3)	C3—C6	1.519 (3)
C1—C4	1.539 (3)	C3—O5	1.441 (3)
C1—O4	1.426 (3)	C4—O1	1.431 (3)
C2—C5	1.518 (3)	C5—O3	1.426 (3)
C2—O2	1.425 (3)	C5—O5	1.403 (3)
C3—C4	1.516 (3)	C6—O3	1.447 (3)
C4—C1—C2	112.51 (18)	C3—C4—C1	111.67 (18)
O4—C1—C2	107.92 (18)	O1—C4—C1	110.28 (17)
O4—C1—C4	110.63 (17)	O1—C4—C3	106.61 (17)
C5—C2—C1	111.30 (19)	O3—C5—C2	110.8 (2)
O2—C2—C1	111.99 (18)	O5—C5—C2	109.82 (19)
O2—C2—C5	109.74 (18)	O5—C5—O3	105.59 (18)
C4—C3—C6	112.70 (19)	O3—C6—C3	103.13 (19)
O5—C3—C4	109.43 (18)	C5—O3—C6	106.85 (17)
O5—C3—C6	101.71 (19)	C5—O5—C3	101.97 (16)