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The crystal structure of phase III of perdeuterocyclohexanone, C6D10O, has been determined at 5 K using high-resolution neutron powder diffraction. Below its melting point of 245 K cyclohexanone forms a plastic crystal in the space group Fm\bar 3m. On cooling below 225 K the crystal transforms to the monoclinic phase III structure in the space group P21/n. The orthorhombic phase II structure exists under high pressure, but the triple point for all three phases is close to atmospheric pressure. Details of the phase II structure are also reported at 4.8 kbar (273 K) and ambient pressure. The phase behaviour of the compound and isotope effects are discussed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768106015485/ws5037sup1.cif
Contains datablock c6d10o_5k

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768106015485/ws5037sup2.rtv
Contains datablock c6d10o_5k

CCDC reference: 618478

Computing details top

Data collection: ISIS Instrument control program (ICP); cell refinement: TOPAS-Academic (Coelho, 2000); data reduction: Standard HRPD normalisation routines; program(s) used to solve structure: TOPAS-Academic (Coelho, 2000); program(s) used to refine structure: TOPAS-Academic (Coelho, 2000); molecular graphics: ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
cyclohexanone top
Crystal data top
C6D10OZ = 4
Mr = 108.14Dx = 1.261 (1) Mg m3
Monoclinic, P21/nMelting point: 245 K
Hall symbol: -P 2ynTime-of-flight neutron radiation, λ = 0.83-9.01 Å
a = 11.7105 (1) ÅT = 5 K
b = 7.1198 (1) ÅParticle morphology: irregular powder
c = 6.8621 (1) Åwhite
β = 95.5627 (3)°cylinder, 25 × 11 mm
V = 569.45 (1) Å3
Data collection top
HRPD
diffractometer
Scan method: tof 20-220 ms
Specimen mounting: standard cylindrical vanadium sample holder
Refinement top
Refinement on F2Profile function: TOPAS TOF Profile function
Least-squares matrix: full99 parameters
Rp = 0.0470 restraints
Rwp = 0.0440 constraints
Rexp = 0.024Weighting scheme based on measured s.u.'s
R(F2) = 0.04306(Δ/σ)max = 0.01
χ2 = 3.460Background function: Shifted Chebyshev function (15 terms)
17807 data pointsPreferred orientation correction: None
Excluded region(s): None
Crystal data top
C6D10Oβ = 95.5627 (3)°
Mr = 108.14V = 569.45 (1) Å3
Monoclinic, P21/nZ = 4
a = 11.7105 (1) ÅTime-of-flight neutron radiation, λ = 0.83-9.01 Å
b = 7.1198 (1) ÅT = 5 K
c = 6.8621 (1) Åcylinder, 25 × 11 mm
Data collection top
HRPD
diffractometer
Scan method: tof 20-220 ms
Specimen mounting: standard cylindrical vanadium sample holder
Refinement top
Rp = 0.047χ2 = 3.460
Rwp = 0.04417807 data points
Rexp = 0.02499 parameters
R(F2) = 0.043060 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O70.70396 (17)0.7017 (3)0.3572 (3)0.0071 (5)*
C10.75931 (19)0.6732 (3)0.2176 (3)0.0089 (4)*
C20.88685 (16)0.6530 (3)0.2397 (3)0.0085 (5)*
C30.94329 (16)0.7724 (3)0.0911 (3)0.0089 (5)*
C40.88839 (18)0.7327 (3)0.1184 (3)0.0085 (5)*
C50.76074 (18)0.7734 (3)0.1324 (3)0.0108 (5)*
C60.70309 (15)0.6520 (3)0.0137 (3)0.0037 (4)*
D210.92000 (17)0.6835 (3)0.3911 (3)0.0187 (6)*
D220.9058 (2)0.5014 (3)0.2145 (3)0.0200 (6)*
D310.93408 (19)0.9220 (4)0.1253 (3)0.0225 (6)*
D321.03528 (19)0.7435 (3)0.1013 (3)0.0174 (6)*
D410.93096 (17)0.8198 (3)0.2199 (3)0.0212 (6)*
D420.90545 (18)0.5869 (3)0.1582 (3)0.0187 (5)*
D510.7481 (2)0.9252 (4)0.1017 (3)0.0215 (6)*
D520.72586 (19)0.7417 (3)0.2819 (3)0.0172 (6)*
D610.61080 (19)0.6835 (3)0.0103 (3)0.0231 (6)*
D620.70943 (19)0.5005 (3)0.0292 (3)0.0222 (6)*
Geometric parameters (Å, º) top
O7—C11.225 (3)C3—D311.098 (4)
C1—C21.494 (3)C3—D321.092 (3)
C1—C61.495 (3)C4—D411.089 (3)
C2—C31.526 (3)C4—D421.097 (3)
C3—C41.543 (3)C5—D511.114 (4)
C4—C51.517 (3)C5—D521.090 (3)
C5—C61.529 (3)C6—D611.102 (3)
C2—D211.095 (3)C6—D621.123 (3)
C2—D221.119 (3)
O7···D52i2.481 (3)D31···D41vi2.470 (3)
O7···D22ii2.515 (3)D32···D42v2.473 (3)
O7···D31iii2.575 (3)D32···O7xi2.739 (3)
O7···D51iii2.612 (3)D32···C5x3.064 (3)
O7···D62ii2.591 (3)D32···D52x2.300 (3)
O7···D32iv2.739 (3)D41···D31vi2.470 (3)
C1···C1iii3.597 (3)D42···D51vii2.588 (3)
C1···C1ii3.597 (3)D42···C2v3.068 (3)
C1···D22ii3.097 (3)D42···D22v2.366 (3)
C2···D42v3.068 (3)D42···D32v2.473 (3)
C3···D31vi3.068 (3)D51···D312.552 (3)
C4···D22v3.055 (3)D51···O7ii2.612 (3)
C5···D51vii3.074 (3)D51···C5viii3.074 (3)
C5···D62viii2.879 (3)D51···D42viii2.588 (3)
C5···D32ix3.064 (3)D51···D52viii2.420 (3)
D21···D61x2.491 (3)D52···O7xii2.481 (3)
D22···O7iii2.515 (3)D52···D51vii2.420 (3)
D22···C1iii3.097 (3)D52···D62viii2.417 (3)
D22···C4v3.055 (3)D52···D32ix2.300 (3)
D22···D42v2.366 (3)D61···D21ix2.491 (3)
D31···D512.552 (3)D62···O7iii2.591 (3)
D31···O7ii2.575 (3)D62···C5vii2.879 (3)
D31···C3vi3.068 (3)D62···D52vii2.417 (3)
O7—C1—C2122.5 (2)D31—C3—D32106.6 (2)
O7—C1—C6122.0 (2)C3—C4—D41108.5 (2)
C2—C1—C6115.51 (17)C3—C4—D42109.6 (2)
C1—C2—C3111.84 (17)C5—C4—D41111.1 (2)
C2—C3—C4110.62 (16)C5—C4—D42111.6 (2)
C3—C4—C5110.07 (17)D41—C4—D42105.9 (2)
C4—C5—C6110.21 (17)C4—C5—D51108.8 (2)
C1—C6—C5111.97 (17)C4—C5—D52107.3 (2)
C1—C2—D21109.7 (2)C6—C5—D51110.4 (2)
C1—C2—D22106.8 (2)C6—C5—D52110.5 (2)
C3—C2—D21112.8 (2)D51—C5—D52109.5 (2)
C3—C2—D22109.2 (2)C1—C6—D61110.0 (2)
D21—C2—D22106.3 (2)C1—C6—D62108.0 (2)
C2—C3—D31109.9 (2)C5—C6—D61111.4 (2)
C2—C3—D32109.9 (2)C5—C6—D62109.1 (2)
C4—C3—D31109.6 (2)D61—C6—D62106.2 (2)
C4—C3—D32110.2 (2)
O7—C1—C2—C3132.3 (2)C1—C2—C3—C452.4 (2)
C6—C1—C2—C349.0 (2)C2—C3—C4—C558.5 (2)
O7—C1—C6—C5131.6 (2)C3—C4—C5—C658.9 (2)
C2—C1—C6—C549.8 (2)C4—C5—C6—C154.0 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+3/2, y+1/2, z+1/2; (iii) x+3/2, y1/2, z+1/2; (iv) x1/2, y+3/2, z+1/2; (v) x+2, y+1, z; (vi) x+2, y+2, z; (vii) x+3/2, y1/2, z1/2; (viii) x+3/2, y+1/2, z1/2; (ix) x1/2, y+3/2, z1/2; (x) x+1/2, y+3/2, z+1/2; (xi) x+1/2, y+3/2, z1/2; (xii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—D22···O7iii1.12 (1)2.52 (1)3.429 (3)138 (1)
C3—D31···O7ii1.10 (1)2.58 (1)3.544 (3)147 (1)
C5—D52···O7xii1.09 (1)2.48 (1)3.538 (3)163 (1)
C6—D62···O7iii1.12 (1)2.59 (1)3.473 (3)135 (1)
Symmetry codes: (ii) x+3/2, y+1/2, z+1/2; (iii) x+3/2, y1/2, z+1/2; (xii) x, y, z1.

Experimental details

Crystal data
Chemical formulaC6D10O
Mr108.14
Crystal system, space groupMonoclinic, P21/n
Temperature (K)5
a, b, c (Å)11.7105 (1), 7.1198 (1), 6.8621 (1)
β (°) 95.5627 (3)
V3)569.45 (1)
Z4
Radiation typeTime-of-flight neutron, λ = 0.83-9.01 Å
Specimen shape, size (mm)Cylinder, 25 × 11
Data collection
DiffractometerHRPD
diffractometer
Specimen mountingStandard cylindrical vanadium sample holder
Data collection mode?
Scan methodTof 20-220 ms
2θ values (°)2θmin = ? 2θmax = ? 2θstep = ?
Refinement
R factors and goodness of fitRp = 0.047, Rwp = 0.044, Rexp = 0.024, R(F2) = 0.04306, χ2 = 3.460
No. of data points17807
No. of parameters99

Computer programs: ISIS Instrument control program (ICP), TOPAS-Academic (Coelho, 2000), Standard HRPD normalisation routines, ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—D22···O7i1.119 (3)2.515 (3)3.429 (3)138.0 (2)
C3—D31···O7ii1.098 (4)2.575 (3)3.544 (3)146.6 (2)
C5—D52···O7iii1.090 (3)2.481 (3)3.538 (3)162.9 (2)
C6—D62···O7i1.123 (3)2.591 (3)3.473 (3)134.62 (18)
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+3/2, y+1/2, z+1/2; (iii) x, y, z1.
Experimental and calculated intra-molecular geometry (Å, 0) for CHO. top
ParameterIII 5 KaII 150 KbMM4c
O7 C11.225 (3)1.221 (3)1.212
C1 C21.494 (3)1.511 (2)1.524
C1 C61.495 (3)1.523 (2)
C2 C31.526 (3)1.541 (3)1.542
C3 C41.543 (3)1.529 (3)1.536
C4 C51.517 (3)1.533 (3)
C5 C61.529 (3)1.542 (3)
<C C>1.517 (3)1.530 (3)1.534
<C H/D>1.102 (3)0.981.112
O7 C1 C2122.5 (2)122.61 (15)122.4
O7 C1 C6122.0 (2)121.93 (15)
C2 C1 C6115.51 (17)115.45 (14)115.1
C1 C2 C3111.84 (17)112.29 (15)110.8
C2 C3 C4110.62 (16)111.63 (15)111.3
C3 C4 C5110.07 (17)110.85 (16)110.8
C4 C5 C6110.21 (17)111.04 (15)
C1 C6 C5111.97 (17)111.65 (13)
O7 C1 C6 C5131.6 (2)132.53 (17)130.9
O7 C1 C2 C3-132.3 (2)-133.44 (17)
C6 C1 C2 C349.0 (2)47.68 (19)51.5
C2 C1 C6 C5-49.8 (2)-48.58 (19)
C2 C3 C4 C558.5 (2)56.8 (2)57.3
C3 C4 C5 C6-58.9 (2)-57.8 (2)
C4 C5 C6 C154.0 (2)52.8 (2)53.4
C1 C2 C3 C4-52.4 (2)-51.1 (2)
a - Phase III this work b - Phase II after Shallard-Brown (2005) libration corrected c - after Langley et al. (2001).
 

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