Polymorphism in cyclohexanol

Ibberson, R.M.; Parsons, S.; Allan, D.R.; Bell, A.M.T.

doi:10.1107/S0108768108025093

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Polymorphism in cyclohexanol

R. M. Ibberson, S. Parsons, D. R. Allan and A. M. T. Bell

The crystal structures and phase behaviour of phase II and the metastable phases III' and III of cyclohexanol, C₆H₁₁OH, have been determined using high-resolution neutron powder, synchrotron X-ray powder and single-crystal X-ray diffraction techniques. Cyclohexanol-II is formed by a transition from the plastic phase I cubic structure at 265 K and crystallizes in a tetragonal structure, space group $P\bar 42_1c$ (Z' = 1), in which the molecules are arranged in a hydrogen-bonded tetrameric ring motif. The structures of phases III' and III are monoclinic, space groups P2₁/c (Z' = 3) and Pc (Z' = 2), respectively, and are characterized by the formation of hydrogen-bonded molecular chains with a threefold-helical and wave-like nature, respectively. Phase III crystallizes at 195 K from a sample of phase I that is supercooled to ca 100 K. Alternatively, phase III may be grown via phase III', the latter transforming from supercooled phase I at ca 200 K. Phase III' is particularly unstable and is metastable with respect to both I and II. Its growth is realised only under very restricted conditions, thus making its characterization especially challenging. The cyclohexanol molecules adopt a chair conformation in all three phases with the hydroxyl groups in an equatorial orientation. No evidence was found indicating hydroxyl groups adopting an axial orientation, contrary to the majority of spectroscopic literature on solid-state cyclohexanol; however, the H atom of the equatorial OH groups is found to adopt both in-plane and out-of-plane orientations.

Keywords: neutron powder diffraction; low-temperature crystallography; hydrogen bonding; phase transitions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768108025093/ws5067sup1.cif Contains datablocks III_120K, II_2K, III_2K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768108025093/ws5067II_2Ksup2.rtv Contains datablock II_2K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768108025093/ws5067III_2Ksup3.rtv Contains datablock III_2K
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768108025093/ws5067III_120Ksup4.fcf Contains datablock III_120K

CCDC references: 705583; 705584; 705585

Computing details top

Data collection: SMART (Bruker-Nonius, 2001) for III_120K. Cell refinement: SAINT (Bruker-Nonius, 2003) for III_120K. Data reduction: SAINT (Bruker-Nonius, 2003) for III_120K. Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for III_120K. Program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003) for III_120K; TOPAS for II_2K, III_2K. Software used to prepare material for publication: PLATON (Spek, 2003) for III_120K.

Figures top

(III_120K) top

Crystal data top

C₆H₁₂O	F(000) = 672
M_r = 100.16	D_x = 1.077 Mg m⁻³
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.68700 Å
Hall symbol: -P 2ybc	Cell parameters from 191 reflections
a = 5.7877 (11) Å	θ = 2–14°
b = 20.267 (5) Å	µ = 0.07 mm⁻¹
c = 15.971 (3) Å	T = 120 K
β = 98.289 (7)°	Cylindrical, colourless
V = 1853.8 (7) Å³	0.2 × 0.2 × 0.1 mm
Z = 12

Data collection top

Bruker SMART diffractometer	399 reflections with I > 2.0σ(I)
Curved silicon monochromator	R_int = 0.266
ω scans	θ_max = 19.1°, θ_min = 1.6°
Absorption correction: multi-scan SADABS (Sheldrick, 2004)	h = −4→4
T_min = 0.77, T_max = 0.98	k = −9→14
1448 measured reflections	l = −12→12
423 independent reflections

Refinement top

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.232	H-atom parameters constrained
wR(F²) = 0.231	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 14.0 -0.901 4.35 4.28
S = 1.09	(Δ/σ)_max = 0.000033
399 reflections	Δρ_max = 0.61 e Å⁻³
85 parameters	Δρ_min = −0.51 e Å⁻³
81 restraints

Crystal data top

C₆H₁₂O	V = 1853.8 (7) Å³
M_r = 100.16	Z = 12
Monoclinic, P2₁/c	Synchrotron radiation, λ = 0.68700 Å
a = 5.7877 (11) Å	µ = 0.07 mm⁻¹
b = 20.267 (5) Å	T = 120 K
c = 15.971 (3) Å	0.2 × 0.2 × 0.1 mm
β = 98.289 (7)°

Data collection top

Bruker SMART diffractometer	423 independent reflections
Absorption correction: multi-scan SADABS (Sheldrick, 2004)	399 reflections with I > 2.0σ(I)
T_min = 0.77, T_max = 0.98	R_int = 0.266
1448 measured reflections	θ_max = 19.1°

Refinement top

R[F² > 2σ(F²)] = 0.232	81 restraints
wR(F²) = 0.231	H-atom parameters constrained
S = 1.09	Δρ_max = 0.61 e Å⁻³
399 reflections	Δρ_min = −0.51 e Å⁻³
85 parameters

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

	x	y	z	U_iso*/U_eq
O11	0.270 (4)	0.2892 (16)	0.6811 (12)	0.073 (5)*
H11	0.1629	0.2575	0.6841	0.0835*
C12	0.241 (5)	0.3589 (17)	0.6913 (17)	0.074 (5)*
H121	0.3401	0.3825	0.6566	0.0850*
C13	−0.013 (5)	0.3701 (16)	0.6554 (15)	0.075 (5)*
H131	−0.1153	0.3453	0.6868	0.0860*
H132	−0.0369	0.3559	0.5968	0.0860*
C14	−0.078 (4)	0.4420 (17)	0.6582 (14)	0.075 (5)*
H141	−0.2433	0.4480	0.6385	0.0860*
H142	0.0127	0.4664	0.6221	0.0860*
C15	−0.020 (5)	0.4693 (17)	0.7448 (16)	0.075 (5)*
H151	−0.0508	0.5165	0.7444	0.0870*
H152	−0.1189	0.4472	0.7802	0.0870*
C16	0.233 (5)	0.4579 (17)	0.7794 (15)	0.075 (5)*
H161	0.2611	0.4738	0.8372	0.0860*
H162	0.3319	0.4817	0.7456	0.0860*
C17	0.294 (4)	0.3858 (18)	0.7783 (14)	0.075 (5)*
H171	0.2013	0.3622	0.8147	0.0860*
H172	0.4585	0.3798	0.7989	0.0860*
O21	−0.638 (4)	0.7370 (13)	0.7109 (12)	0.047 (5)*
H21	−0.5180	0.7545	0.7462	0.0502*
C22	−0.596 (4)	0.6939 (14)	0.6432 (14)	0.048 (5)*
H221	−0.7339	0.6988	0.6001	0.0540*
C23	−0.595 (4)	0.6228 (14)	0.6660 (12)	0.049 (5)*
H231	−0.7348	0.6111	0.6899	0.0540*
H232	−0.4583	0.6155	0.7078	0.0540*
C24	−0.578 (4)	0.5800 (12)	0.5895 (14)	0.049 (5)*
H241	−0.7201	0.5850	0.5496	0.0540*
H242	−0.5603	0.5343	0.6073	0.0540*
C25	−0.369 (4)	0.5978 (12)	0.5485 (14)	0.049 (5)*
H251	−0.2258	0.5888	0.5864	0.0550*
H252	−0.3719	0.5719	0.4971	0.0550*
C26	−0.369 (4)	0.6692 (13)	0.5263 (12)	0.049 (5)*
H261	−0.5040	0.6774	0.4835	0.0550*
H262	−0.2272	0.6807	0.5038	0.0550*
C27	−0.386 (4)	0.7117 (12)	0.6029 (15)	0.049 (5)*
H271	−0.4038	0.7574	0.5854	0.0540*
H272	−0.2443	0.7069	0.6433	0.0540*
O31	−0.950 (4)	0.8036 (17)	0.3123 (13)	0.074 (5)*
H31	−0.8443	0.7902	0.2798	0.0818*
C32	−0.845 (5)	0.8213 (15)	0.4013 (15)	0.075 (5)*
H321	−0.7569	0.7838	0.4279	0.0830*
C33	−1.031 (3)	0.8408 (17)	0.4517 (16)	0.075 (5)*
H331	−1.1264	0.8760	0.4237	0.0840*
H332	−1.1283	0.8027	0.4582	0.0840*
C34	−0.928 (5)	0.8661 (17)	0.5374 (13)	0.075 (5)*
H341	−1.0502	0.8804	0.5690	0.0840*
H342	−0.8417	0.8299	0.5669	0.0840*
C35	−0.763 (4)	0.9225 (15)	0.5303 (15)	0.076 (5)*
H351	−0.8518	0.9600	0.5053	0.0840*
H352	−0.6869	0.9340	0.5865	0.0840*
C36	−0.578 (3)	0.9038 (18)	0.4792 (16)	0.076 (5)*
H361	−0.4852	0.9427	0.4721	0.0840*
H362	−0.4798	0.8694	0.5075	0.0840*
C37	−0.681 (5)	0.8776 (17)	0.3935 (13)	0.075 (5)*
H371	−0.7658	0.9134	0.3629	0.0830*
H372	−0.5577	0.8626	0.3628	0.0830*

Geometric parameters (Å, º) top

O31—C32	1.51 (3)	O11—H11	0.900
O31—H31	0.900	C27—C26	1.510 (16)
C37—C32	1.502 (16)	C27—C22	1.500 (16)
C37—C36	1.507 (16)	C27—H271	0.970
C37—H371	0.970	C27—H272	0.970
C37—H372	0.970	C25—C24	1.500 (16)
C34—C33	1.503 (16)	C25—C26	1.491 (16)
C34—C35	1.501 (16)	C25—H251	0.971
C34—H341	0.970	C25—H252	0.971
C34—H342	0.970	C24—C23	1.513 (16)
C15—C14	1.483 (16)	C24—H241	0.971
C15—C16	1.506 (16)	C24—H242	0.970
C15—H151	0.971	C32—C33	1.485 (16)
C15—H152	0.970	C32—H321	0.979
C14—C13	1.510 (17)	C12—H121	0.979
C14—H141	0.969	C33—H331	0.970
C14—H142	0.970	C33—H332	0.971
C13—C12	1.514 (16)	C35—C36	1.486 (16)
C13—H131	0.970	C35—H351	0.971
C13—H132	0.970	C35—H352	0.970
O21—C22	1.44 (3)	C36—H361	0.971
O21—H21	0.900	C36—H362	0.970
C16—C17	1.504 (17)	C26—H261	0.973
C16—H161	0.969	C26—H262	0.972
C16—H162	0.970	C23—C22	1.487 (16)
C17—C12	1.484 (17)	C23—H231	0.971
C17—H171	0.970	C23—H232	0.972
C17—H172	0.971	C22—H221	0.981
O11—C12	1.43 (4)

C32—O31—H31	113.6	H251—C25—H252	109.5
C32—C37—C36	111.3 (8)	C25—C24—C23	111.5 (8)
C32—C37—H371	109.2	C25—C24—H241	110.4
C36—C37—H371	107.4	C23—C24—H241	108.7
C32—C37—H372	109.0	C25—C24—H242	107.5
C36—C37—H372	110.3	C23—C24—H242	109.1
H371—C37—H372	109.6	H241—C24—H242	109.6
C33—C34—C35	111.4 (8)	O31—C32—C37	106 (2)
C33—C34—H341	110.6	O31—C32—C33	111 (2)
C35—C34—H341	109.4	C37—C32—C33	111.1 (8)
C33—C34—H342	107.0	O31—C32—H321	109.7
C35—C34—H342	108.9	C37—C32—H321	109.1
H341—C34—H342	109.6	C33—C32—H321	110.3
C14—C15—C16	111.3 (8)	C13—C12—C17	111.0 (8)
C14—C15—H151	110.1	C13—C12—O11	103 (2)
C16—C15—H151	108.7	C17—C12—O11	117 (2)
C14—C15—H152	107.2	C13—C12—H121	109.2
C16—C15—H152	109.9	C17—C12—H121	106.9
H151—C15—H152	109.6	O11—C12—H121	109.2
C15—C14—C13	111.4 (8)	C34—C33—C32	111.1 (8)
C15—C14—H141	109.8	C34—C33—H331	107.0
C13—C14—H141	110.5	C32—C33—H331	110.8
C15—C14—H142	107.1	C34—C33—H332	109.5
C13—C14—H142	108.3	C32—C33—H332	108.8
H141—C14—H142	109.7	H331—C33—H332	109.6
C14—C13—C12	111.5 (8)	C34—C35—C36	111.3 (8)
C14—C13—H131	108.1	C34—C35—H351	108.9
C12—C13—H131	111.0	C36—C35—H351	110.6
C14—C13—H132	108.3	C34—C35—H352	108.9
C12—C13—H132	108.5	C36—C35—H352	107.6
H131—C13—H132	109.5	H351—C35—H352	109.6
C22—O21—H21	120.8	C37—C36—C35	111.7 (8)
C15—C16—C17	111.1 (8)	C37—C36—H361	109.5
C15—C16—H161	108.6	C35—C36—H361	108.3
C17—C16—H161	109.0	C37—C36—H362	107.4
C15—C16—H162	109.9	C35—C36—H362	110.4
C17—C16—H162	108.6	H361—C36—H362	109.7
H161—C16—H162	109.6	C27—C26—C25	111.0 (8)
C16—C17—C12	110.6 (9)	C27—C26—H261	109.6
C16—C17—H171	108.8	C25—C26—H261	107.7
C12—C17—H171	108.9	C27—C26—H262	108.6
C16—C17—H172	109.7	C25—C26—H262	110.4
C12—C17—H172	109.3	H261—C26—H262	109.5
H171—C17—H172	109.5	C24—C23—C22	110.9 (8)
C12—O11—H11	127.0	C24—C23—H231	109.5
C26—C27—C22	111.1 (8)	C22—C23—H231	111.2
C26—C27—H271	109.1	C24—C23—H232	108.9
C22—C27—H271	107.0	C22—C23—H232	106.8
C26—C27—H272	109.6	H231—C23—H232	109.5
C22—C27—H272	110.5	C27—C22—C23	111.3 (8)
H271—C27—H272	109.5	C27—C22—O21	114 (2)
C24—C25—C26	111.4 (8)	C23—C22—O21	114 (2)
C24—C25—H251	110.6	C27—C22—H221	107.7
C26—C25—H251	107.6	C23—C22—H221	104.0
C24—C25—H252	108.8	O21—C22—H221	105.0
C26—C25—H252	108.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O31ⁱ	0.90	1.75	2.651 (2)	179
O21—H21···O11ⁱⁱ	0.90	1.85	2.749 (2)	179
O31—H31···O21ⁱⁱⁱ	0.90	1.82	2.723 (2)	178

Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2; (iii) x, −y+3/2, z−1/2.

(II_2K) perdeutero cyclohexanol top

Crystal data top

C₆D₁₂O	Z = 8
M_r = 112.23	D_x = 1.271 Mg m⁻³
Tetragonal, P42₁c	Melting point: 298 K
a = 10.53507 (3) Å	Neutron radiation, λ = ? Å
c = 10.53715 (6) Å	T = 2 K
V = 1169.49 (1) Å³	× × mm

Data collection top

HRPD diffractometer	k = ?→?
h = ?→?	l = ?→?

Refinement top

Least-squares matrix: full	2 restraints
S = 1.15	(Δ/σ)_max = 0.03
76 parameters

Crystal data top

C₆D₁₂O	V = 1169.49 (1) Å³
M_r = 112.23	Z = 8
Tetragonal, P42₁c	Neutron radiation, λ = ? Å
a = 10.53507 (3) Å	T = 2 K
c = 10.53715 (6) Å	× × mm

Data collection top

HRPD
diffractometer

Refinement top

S = 1.15	2 restraints
76 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	−0.1270 (5)	−0.6423 (4)	0.0952 (4)	0.0035 (3)*
C2	−0.1983 (4)	−0.5627 (4)	0.1935 (5)	0.0035 (3)*
C3	−0.3396 (4)	−0.5675 (4)	0.1716 (4)	0.0035 (3)*
C4	−0.3857 (4)	−0.7063 (4)	0.1694 (4)	0.0035 (3)*
C5	−0.3125 (4)	−0.7808 (4)	0.0701 (5)	0.0035 (3)*
C6	−0.1743 (4)	−0.7771 (5)	0.0964 (4)	0.0035 (3)*
D11	−0.0249 (5)	−0.6403 (6)	0.1138 (5)	0.0178 (4)*
D12	−0.1408 (5)	−0.6015 (5)	−0.0033 (6)	0.0178 (4)*
D21	−0.1626 (5)	−0.4631 (4)	0.1949 (6)	0.0178 (4)*
D22	−0.1797 (5)	−0.6008 (5)	0.2898 (5)	0.0178 (4)*
D31	−0.3629 (5)	−0.5200 (5)	0.0847 (5)	0.0178 (4)*
D32	−0.3910 (5)	−0.5173 (6)	0.2471 (5)	0.0178 (4)*
D41	−0.4892 (5)	−0.7100 (6)	0.1489 (5)	0.0178 (4)*
D42	−0.3759 (5)	−0.7456 (5)	0.2661 (5)	0.0178 (4)*
D51	−0.3323 (5)	−0.7476 (7)	−0.0263 (5)	0.0178 (4)*
D52	−0.3494 (5)	−0.8792 (5)	0.0679 (4)	0.0178 (4)*
D62	−0.1571 (5)	−0.8225 (4)	0.1883 (5)	0.0178 (4)*
D71	−0.1318 (9)	−0.9335 (9)	−0.0025 (8)	0.028 (2)*	0.729 (13)
O61	−0.1021 (5)	−0.8456 (7)	−0.0002 (6)	0.0087 (14)*
D72	−0.0174 (13)	−0.871 (2)	0.011 (2)	0.028 (2)*	0.271 (13)

Geometric parameters (Å, º) top

C1—C2	1.530 (5)	C6—C1	1.505 (6)
C1—C6	1.505 (6)	C6—C5	1.483 (6)
C1—D11	1.094 (6)	C6—D62	1.096 (7)
C1—D12	1.132 (7)	C6—O61	1.461 (7)
C2—C1	1.530 (5)	D11—C1	1.094 (6)
C2—C3	1.507 (6)	D12—C1	1.132 (7)
C2—D21	1.115 (5)	D21—C2	1.115 (5)
C2—D22	1.109 (6)	D22—C2	1.109 (6)
C3—C2	1.507 (6)	D31—C3	1.072 (6)
C3—C4	1.541 (5)	D32—C3	1.099 (6)
C3—D31	1.072 (6)	D41—C4	1.112 (5)
C3—D32	1.099 (6)	D42—C4	1.105 (7)
C4—C3	1.541 (5)	D51—C5	1.094 (7)
C4—C5	1.518 (5)	D52—C5	1.107 (5)
C4—D41	1.112 (5)	D62—C6	1.096 (7)
C4—D42	1.105 (7)	D71—O61	0.977 (7)
C5—C4	1.518 (5)	O61—C6	1.461 (7)
C5—C6	1.483 (6)	O61—D71	0.977 (7)
C5—D51	1.094 (7)	O61—D72	0.938 (11)
C5—D52	1.107 (5)

C2—C1—C6	110.4 (4)	C3—C4—C5	109.9 (4)
C2—C1—D11	110.5 (4)	C3—C4—D41	110.2 (5)
C2—C1—D12	110.5 (5)	C3—C4—D42	108.2 (4)
C6—C1—D11	110.0 (5)	C5—C4—D41	110.2 (5)
C6—C1—D12	108.8 (5)	C5—C4—D42	113.2 (5)
D11—C1—D12	106.5 (6)	D41—C4—D42	104.9 (5)
C1—C2—C3	111.3 (4)	C4—C5—C6	110.9 (4)
C1—C2—D21	111.0 (5)	C4—C5—D51	112.2 (5)
C1—C2—D22	109.6 (4)	C4—C5—D52	108.6 (5)
C3—C2—D21	111.5 (5)	C6—C5—D51	110.6 (6)
C3—C2—D22	107.6 (5)	C6—C5—D52	111.9 (5)
D21—C2—D22	105.6 (7)	D51—C5—D52	102.3 (6)
C2—C3—C4	110.2 (3)	C1—C6—C5	110.4 (4)
C2—C3—D31	109.9 (5)	C1—C6—D62	111.4 (5)
C2—C3—D32	111.1 (5)	C1—C6—O61	106.8 (4)
C4—C3—D31	111.1 (4)	C5—C6—D62	108.4 (5)
C4—C3—D32	108.2 (5)	C5—C6—O61	111.6 (4)
D31—C3—D32	106.3 (5)	D62—C6—O61	108.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O61—D71···O61ⁱ	0.98 (1)	1.79 (1)	2.758 (9)	169 (1)
O61—D72···O61ⁱⁱ	0.94 (2)	1.84 (2)	2.758 (9)	167 (2)

Symmetry codes: (i) −y−1, x−1, −z; (ii) y+1, −x−1, −z.

(III_2K) perdeutero cyclohexanol top

Crystal data top

C₆D₁₂O	V = 590.93 (1) Å³
M_r = 112.23	Z = 4
Monoclinic, Pc	D_x = 1.261 Mg m⁻³
Hall symbol: P -2yc	Melting point: 298 K
a = 12.0244 (2) Å	Neutron radiation, λ = ? Å
b = 6.36200 (12) Å	T = 2 K
c = 8.10998 (18) Å	× × mm
β = 107.7331 (18)°

Data collection top

HRPD diffractometer	k = ?→?
h = ?→?	l = ?→?

Refinement top

Least-squares matrix: full	0 restraints
S = 2.29	(Δ/σ)_max = 0.03
16 parameters

Crystal data top

C₆D₁₂O	β = 107.7331 (18)°
M_r = 112.23	V = 590.93 (1) Å³
Monoclinic, Pc	Z = 4
a = 12.0244 (2) Å	Neutron radiation, λ = ? Å
b = 6.36200 (12) Å	T = 2 K
c = 8.10998 (18) Å	× × mm

Data collection top

HRPD
diffractometer

Refinement top

S = 2.29	0 restraints
16 parameters

Special details top

Refinement. The two molecules comprising the asymmetric unit were refined as rigid bodies with common intramolecular bond length and bond angle parameters. Based on the e.s.d.s associated with the translational and rotational variables for each body, bond length and angle e.s.d s are typically 0.005 Å and 0.07 ° respectively. Parameters associated with the two hydroxyl groups (O—H bond length, C—O—H bond angle and H—O—C—C torsional angle) were defined as refinable paramters and their e.s.d. values are reported below.

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

	x	y	z	U_iso*/U_eq
C11	0.44022	0.27581	0.18713	0.0063 (4)*
C12	0.52225	0.45863	0.18709	0.0063 (4)*
C13	0.6474	0.39674	0.28574	0.0063 (4)*
C14	0.68323	0.20529	0.20048	0.0063 (4)*
C15	0.60121	0.02257	0.20028	0.0063 (4)*
C16	0.47604	0.08437	0.10168	0.0063 (4)*
O11	0.32258	0.33719	0.0997	0.0091 (4)*
D111	0.44491	0.23707	0.32002	0.0181 (4)*
D121	0.49707	0.59438	0.24961	0.0181 (4)*
D122	0.51684	0.49838	0.05424	0.0181 (4)*
D131	0.65334	0.35873	0.41923	0.0181 (4)*
D132	0.70581	0.52718	0.28397	0.0181 (4)*
D141	0.77238	0.16063	0.27222	0.0181 (4)*
D142	0.67845	0.2435	0.06733	0.0181 (4)*
D151	0.60658	−0.01745	0.33319	0.0181 (4)*
D152	0.62642	−0.11325	0.13786	0.0181 (4)*
D161	0.41762	−0.0461	0.10329	0.0181 (4)*
D162	0.47009	0.12228	−0.03183	0.0181 (4)*
D11	0.30724	0.46328	0.16489	0.0290 (4)*
C21	0.14493	0.27554	0.66548	0.0063 (4)*
C22	0.06787	0.45848	0.68477	0.0063 (4)*
C23	−0.06023	0.40268	0.59995	0.0063 (4)*
C24	−0.09121	0.20679	0.68537	0.0063 (4)*
C25	−0.01414	0.02395	0.66634	0.0063 (4)*
C26	0.11397	0.07965	0.75109	0.0063 (4)*
O21	0.26503	0.33148	0.73988	0.0091 (4)*
D211	0.13099	0.24431	0.52849	0.0181 (4)*
D221	0.08948	0.59749	0.62211	0.0181 (4)*
D222	0.08251	0.49071	0.82164	0.0181 (4)*
D231	−0.07541	0.37222	0.46257	0.0181 (4)*
D232	−0.11498	0.5331	0.61548	0.0181 (4)*
D241	−0.18256	0.16656	0.62343	0.0261 (7)*
D242	−0.07717	0.23747	0.82259	0.0181 (4)*
D251	−0.02875	−0.00856	0.52938	0.0181 (4)*
D252	−0.03578	−0.11513	0.72889	0.0181 (4)*
D261	0.16875	−0.05081	0.73572	0.0181 (4)*
D262	0.12916	0.11001	0.88849	0.0181 (4)*
D21	0.28744	0.33853	0.8701	0.0290 (4)*

Geometric parameters (Å, º) top

C11—C12	1.525	C21—C22	1.525
C11—C16	1.526	C21—C26	1.526
C11—O11	1.430	C21—O21	1.430
C11—D111	1.090	C21—D211	1.090
C11—D11	1.958	C22—C21	1.525
C12—C11	1.525	C22—C23	1.525
C12—C13	1.525	C22—D221	1.090
C12—D121	1.090	C22—D222	1.089
C12—D122	1.089	C23—C22	1.525
C13—C12	1.525	C23—C24	1.526
C13—C14	1.526	C23—D231	1.090
C13—D131	1.090	C23—D232	1.090
C13—D132	1.090	C24—C23	1.526
C14—C13	1.526	C24—C25	1.524
C14—C15	1.524	C24—D241	1.090
C14—D141	1.090	C24—D242	1.091
C14—D142	1.091	C25—C24	1.524
C15—C14	1.524	C25—C26	1.525
C15—C16	1.525	C25—D251	1.090
C15—D151	1.090	C25—D252	1.090
C15—D152	1.090	C26—C21	1.526
C16—C11	1.526	C26—C25	1.525
C16—C15	1.525	C26—D261	1.090
C16—D161	1.090	C26—D262	1.090
C16—D162	1.090	O21—D11ⁱ	1.587
O11—C11	1.430	O21—C21	1.430
O11—D11	1.008	O21—D21	1.008
D111—C11	1.090	D211—C21	1.090
D121—C12	1.090	D221—C22	1.090
D122—C12	1.089	D222—C22	1.089
D131—C13	1.090	D231—C23	1.090
D132—C13	1.090	D232—C23	1.090
D141—C14	1.090	D241—C24	1.090
D142—C14	1.091	D242—C24	1.091
D151—C15	1.090	D251—C25	1.090
D152—C15	1.090	D252—C25	1.090
D161—C16	1.090	D261—C26	1.090
D162—C16	1.090	D262—C26	1.090
D11—O11	1.008	D21—O21	1.008

C12—C11—C16	109.65	C22—C21—O21	109.49
C12—C11—O11	109.49	C22—C21—D211	109.51
C12—C11—D111	109.50	C26—C21—O21	111.46
C16—C11—O11	111.46	C26—C21—D211	109.36
C16—C11—D111	109.36	O21—C21—D211	107.30
O11—C11—D111	107.30	C21—C22—C23	109.74
C11—C12—C13	109.74	C21—C22—D221	109.43
C11—C12—D121	109.44	C21—C22—D222	109.48
C11—C12—D122	109.48	C23—C22—D221	109.26
C13—C12—D121	109.26	C23—C22—D222	109.33
C13—C12—D122	109.32	D221—C22—D222	109.56
D121—C12—D122	109.56	C22—C23—C24	109.75
C12—C13—C14	109.75	C22—C23—D231	109.51
C12—C13—D131	109.50	C22—C23—D232	109.46
C12—C13—D132	109.46	C24—C23—D231	109.31
C14—C13—D131	109.31	C24—C23—D232	109.24
C14—C13—D132	109.25	D231—C23—D232	109.53
D131—C13—D132	109.53	C23—C24—C25	109.71
C13—C14—C15	109.71	C23—C24—D241	109.48
C13—C14—D141	109.48	C23—C24—D242	109.48
C13—C14—D142	109.48	C25—C24—D241	109.42
C15—C14—D141	109.42	C25—C24—D242	109.25
C15—C14—D142	109.25	D241—C24—D242	109.46
D141—C14—D142	109.45	C24—C25—C26	109.80
C14—C15—C16	109.80	C24—C25—D251	109.49
C14—C15—D151	109.48	C24—C25—D252	109.49
C14—C15—D152	109.49	C26—C25—D251	109.29
C16—C15—D151	109.29	C26—C25—D252	109.29
C16—C15—D152	109.29	D251—C25—D252	109.44
D151—C15—D152	109.44	C21—C26—C25	109.71
C11—C16—C15	109.72	C21—C26—D261	109.26
C11—C16—D161	109.27	C21—C26—D262	109.39
C11—C16—D162	109.39	C25—C26—D261	109.51
C15—C16—D161	109.51	C25—C26—D262	109.48
C15—C16—D162	109.48	D261—C26—D262	109.44
D161—C16—D162	109.43	D11ⁱ—O21—C21	116.26
C11—O11—D11	105.58	D11ⁱ—O21—D21	110.48
O11—D11—O21ⁱⁱ	170.46	C21—O21—D21	111.49
C22—C21—C26	109.65

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+1, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—D11···O21ⁱⁱ	1.01 (1)	1.59 (1)	2.587 (9)	171 (1)
O21—D21···O11ⁱⁱⁱ	1.01 (1)	1.78 (1)	2.787 (9)	177 (1)

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) x, y, z+1.

Experimental details

	(III_120K)	(II_2K)	(III_2K)
Crystal data
Chemical formula	C₆H₁₂O	C₆D₁₂O	C₆D₁₂O
M_r	100.16	112.23	112.23
Crystal system, space group	Monoclinic, P2₁/c	Tetragonal, P42₁c	Monoclinic, Pc
Temperature (K)	120	2	2
a, b, c (Å)	5.7877 (11), 20.267 (5), 15.971 (3)	10.53507 (3), 10.535067, 10.53715 (6)	12.0244 (2), 6.36200 (12), 8.10998 (18)
α, β, γ (°)	90, 98.289 (7), 90	90, 90, 90	90, 107.7331 (18), 90
V (Å³)	1853.8 (7)	1169.49 (1)	590.93 (1)
Z	12	8	4
Radiation type	Synchrotron, λ = 0.68700 Å	Neutron, λ = ? Å	Neutron, λ = ? Å
µ (mm⁻¹)	0.07	?	?
Crystal size (mm)	0.2 × 0.2 × 0.1	× ×	× ×

Data collection
Diffractometer	Bruker SMART diffractometer	HRPD diffractometer	HRPD diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 2004)	? No correction is applied.	? No correction is applied.
T_min, T_max	0.77, 0.98	1.000, 1.000	1.000, 1.000
No. of measured, independent and observed reflections	1448, 423, 399 [I > 2.0σ(I)]	?, ?, ? (?)	?, ?, ? (?)
R_int	0.266	?	?
θ_max (°)	19.1	?	?
(sin θ/λ)_max (Å⁻¹)	0.477	–	–

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.232, 0.231, 1.09	?, ?, 1.15	?, ?, 2.29
No. of reflections	399	?	?
No. of parameters	85	76	16
No. of restraints	81	2	0
H-atom treatment	H-atom parameters constrained	–	–
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.51	?, ?	?, ?

Computer programs: SMART (Bruker-Nonius, 2001), SAINT (Bruker-Nonius, 2003), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), TOPAS, PLATON (Spek, 2003).

Selected geometric parameters (Å, º) for (III_120K) top

O31—C32	1.51 (3)	C17—C12	1.484 (17)
C37—C32	1.502 (16)	O11—C12	1.43 (4)
C37—C36	1.507 (16)	C27—C26	1.510 (16)
C34—C33	1.503 (16)	C27—C22	1.500 (16)
C34—C35	1.501 (16)	C25—C24	1.500 (16)
C15—C14	1.483 (16)	C25—C26	1.491 (16)
C15—C16	1.506 (16)	C24—C23	1.513 (16)
C14—C13	1.510 (17)	C32—C33	1.485 (16)
C13—C12	1.514 (16)	C35—C36	1.486 (16)
O21—C22	1.44 (3)	C23—C22	1.487 (16)
C16—C17	1.504 (17)

C32—C37—C36	111.3 (8)	C37—C32—C33	111.1 (8)
C33—C34—C35	111.4 (8)	C13—C12—C17	111.0 (8)
C14—C15—C16	111.3 (8)	C13—C12—O11	103 (2)
C15—C14—C13	111.4 (8)	C17—C12—O11	117 (2)
C14—C13—C12	111.5 (8)	C34—C33—C32	111.1 (8)
C15—C16—C17	111.1 (8)	C34—C35—C36	111.3 (8)
C16—C17—C12	110.6 (9)	C37—C36—C35	111.7 (8)
C26—C27—C22	111.1 (8)	C27—C26—C25	111.0 (8)
C24—C25—C26	111.4 (8)	C24—C23—C22	110.9 (8)
C25—C24—C23	111.5 (8)	C27—C22—C23	111.3 (8)
O31—C32—C37	106 (2)	C27—C22—O21	114 (2)
O31—C32—C33	111 (2)	C23—C22—O21	114 (2)

Hydrogen-bond geometry (Å, º) for (III_120K) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O31ⁱ	0.90	1.75	2.651 (2)	179
O21—H21···O11ⁱⁱ	0.90	1.85	2.749 (2)	179
O31—H31···O21ⁱⁱⁱ	0.90	1.82	2.723 (2)	178

Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2; (iii) x, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) for (II_2K) top

D—H···A	D—H	H···A	D···A	D—H···A
O61—D71···O61ⁱ	0.978 (12)	1.792 (11)	2.758 (9)	168.7 (9)
O61—D72···O61ⁱⁱ	0.939 (16)	1.836 (16)	2.758 (9)	166.7 (19)

Symmetry codes: (i) −y−1, x−1, −z; (ii) y+1, −x−1, −z.

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