The crystal structure of phase III of perdeuterocyclohexanone, C
6D
10O, 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
Fmm. On cooling below 225 K the crystal transforms to the monoclinic phase III structure in the space group
P2
1/
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
CCDC reference: 618478
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).
Crystal data top
C6D10O | Z = 4 |
Mr = 108.14 | Dx = 1.261 (1) Mg m−3 |
Monoclinic, P21/n | Melting point: 245 K |
Hall symbol: -P 2yn | Time-of-flight neutron radiation, λ = 0.83-9.01 Å |
a = 11.7105 (1) Å | T = 5 K |
b = 7.1198 (1) Å | Particle morphology: irregular powder |
c = 6.8621 (1) Å | white |
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 F2 | Profile function: TOPAS TOF Profile function |
Least-squares matrix: full | 99 parameters |
Rp = 0.047 | 0 restraints |
Rwp = 0.044 | 0 constraints |
Rexp = 0.024 | Weighting scheme based on measured s.u.'s |
R(F2) = 0.04306 | (Δ/σ)max = 0.01 |
χ2 = 3.460 | Background function: Shifted Chebyshev function (15 terms) |
17807 data points | Preferred orientation correction: None |
Excluded region(s): None | |
Crystal data top
C6D10O | β = 95.5627 (3)° |
Mr = 108.14 | V = 569.45 (1) Å3 |
Monoclinic, P21/n | Z = 4 |
a = 11.7105 (1) Å | Time-of-flight neutron radiation, λ = 0.83-9.01 Å |
b = 7.1198 (1) Å | T = 5 K |
c = 6.8621 (1) Å | cylinder, 25 × 11 mm |
Data collection top
HRPD diffractometer | Scan method: tof 20-220 ms |
Specimen mounting: standard cylindrical vanadium sample holder | |
Refinement top
Rp = 0.047 | χ2 = 3.460 |
Rwp = 0.044 | 17807 data points |
Rexp = 0.024 | 99 parameters |
R(F2) = 0.04306 | 0 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O7 | 0.70396 (17) | 0.7017 (3) | 0.3572 (3) | 0.0071 (5)* | |
C1 | 0.75931 (19) | 0.6732 (3) | 0.2176 (3) | 0.0089 (4)* | |
C2 | 0.88685 (16) | 0.6530 (3) | 0.2397 (3) | 0.0085 (5)* | |
C3 | 0.94329 (16) | 0.7724 (3) | 0.0911 (3) | 0.0089 (5)* | |
C4 | 0.88839 (18) | 0.7327 (3) | −0.1184 (3) | 0.0085 (5)* | |
C5 | 0.76074 (18) | 0.7734 (3) | −0.1324 (3) | 0.0108 (5)* | |
C6 | 0.70309 (15) | 0.6520 (3) | 0.0137 (3) | 0.0037 (4)* | |
D21 | 0.92000 (17) | 0.6835 (3) | 0.3911 (3) | 0.0187 (6)* | |
D22 | 0.9058 (2) | 0.5014 (3) | 0.2145 (3) | 0.0200 (6)* | |
D31 | 0.93408 (19) | 0.9220 (4) | 0.1253 (3) | 0.0225 (6)* | |
D32 | 1.03528 (19) | 0.7435 (3) | 0.1013 (3) | 0.0174 (6)* | |
D41 | 0.93096 (17) | 0.8198 (3) | −0.2199 (3) | 0.0212 (6)* | |
D42 | 0.90545 (18) | 0.5869 (3) | −0.1582 (3) | 0.0187 (5)* | |
D51 | 0.7481 (2) | 0.9252 (4) | −0.1017 (3) | 0.0215 (6)* | |
D52 | 0.72586 (19) | 0.7417 (3) | −0.2819 (3) | 0.0172 (6)* | |
D61 | 0.61080 (19) | 0.6835 (3) | 0.0103 (3) | 0.0231 (6)* | |
D62 | 0.70943 (19) | 0.5005 (3) | −0.0292 (3) | 0.0222 (6)* | |
Geometric parameters (Å, º) top
O7—C1 | 1.225 (3) | C3—D31 | 1.098 (4) |
C1—C2 | 1.494 (3) | C3—D32 | 1.092 (3) |
C1—C6 | 1.495 (3) | C4—D41 | 1.089 (3) |
C2—C3 | 1.526 (3) | C4—D42 | 1.097 (3) |
C3—C4 | 1.543 (3) | C5—D51 | 1.114 (4) |
C4—C5 | 1.517 (3) | C5—D52 | 1.090 (3) |
C5—C6 | 1.529 (3) | C6—D61 | 1.102 (3) |
C2—D21 | 1.095 (3) | C6—D62 | 1.123 (3) |
C2—D22 | 1.119 (3) | | |
| | | |
O7···D52i | 2.481 (3) | D31···D41vi | 2.470 (3) |
O7···D22ii | 2.515 (3) | D32···D42v | 2.473 (3) |
O7···D31iii | 2.575 (3) | D32···O7xi | 2.739 (3) |
O7···D51iii | 2.612 (3) | D32···C5x | 3.064 (3) |
O7···D62ii | 2.591 (3) | D32···D52x | 2.300 (3) |
O7···D32iv | 2.739 (3) | D41···D31vi | 2.470 (3) |
C1···C1iii | 3.597 (3) | D42···D51vii | 2.588 (3) |
C1···C1ii | 3.597 (3) | D42···C2v | 3.068 (3) |
C1···D22ii | 3.097 (3) | D42···D22v | 2.366 (3) |
C2···D42v | 3.068 (3) | D42···D32v | 2.473 (3) |
C3···D31vi | 3.068 (3) | D51···D31 | 2.552 (3) |
C4···D22v | 3.055 (3) | D51···O7ii | 2.612 (3) |
C5···D51vii | 3.074 (3) | D51···C5viii | 3.074 (3) |
C5···D62viii | 2.879 (3) | D51···D42viii | 2.588 (3) |
C5···D32ix | 3.064 (3) | D51···D52viii | 2.420 (3) |
D21···D61x | 2.491 (3) | D52···O7xii | 2.481 (3) |
D22···O7iii | 2.515 (3) | D52···D51vii | 2.420 (3) |
D22···C1iii | 3.097 (3) | D52···D62viii | 2.417 (3) |
D22···C4v | 3.055 (3) | D52···D32ix | 2.300 (3) |
D22···D42v | 2.366 (3) | D61···D21ix | 2.491 (3) |
D31···D51 | 2.552 (3) | D62···O7iii | 2.591 (3) |
D31···O7ii | 2.575 (3) | D62···C5vii | 2.879 (3) |
D31···C3vi | 3.068 (3) | D62···D52vii | 2.417 (3) |
| | | |
O7—C1—C2 | 122.5 (2) | D31—C3—D32 | 106.6 (2) |
O7—C1—C6 | 122.0 (2) | C3—C4—D41 | 108.5 (2) |
C2—C1—C6 | 115.51 (17) | C3—C4—D42 | 109.6 (2) |
C1—C2—C3 | 111.84 (17) | C5—C4—D41 | 111.1 (2) |
C2—C3—C4 | 110.62 (16) | C5—C4—D42 | 111.6 (2) |
C3—C4—C5 | 110.07 (17) | D41—C4—D42 | 105.9 (2) |
C4—C5—C6 | 110.21 (17) | C4—C5—D51 | 108.8 (2) |
C1—C6—C5 | 111.97 (17) | C4—C5—D52 | 107.3 (2) |
C1—C2—D21 | 109.7 (2) | C6—C5—D51 | 110.4 (2) |
C1—C2—D22 | 106.8 (2) | C6—C5—D52 | 110.5 (2) |
C3—C2—D21 | 112.8 (2) | D51—C5—D52 | 109.5 (2) |
C3—C2—D22 | 109.2 (2) | C1—C6—D61 | 110.0 (2) |
D21—C2—D22 | 106.3 (2) | C1—C6—D62 | 108.0 (2) |
C2—C3—D31 | 109.9 (2) | C5—C6—D61 | 111.4 (2) |
C2—C3—D32 | 109.9 (2) | C5—C6—D62 | 109.1 (2) |
C4—C3—D31 | 109.6 (2) | D61—C6—D62 | 106.2 (2) |
C4—C3—D32 | 110.2 (2) | | |
| | | |
O7—C1—C2—C3 | −132.3 (2) | C1—C2—C3—C4 | −52.4 (2) |
C6—C1—C2—C3 | 49.0 (2) | C2—C3—C4—C5 | 58.5 (2) |
O7—C1—C6—C5 | 131.6 (2) | C3—C4—C5—C6 | −58.9 (2) |
C2—C1—C6—C5 | −49.8 (2) | C4—C5—C6—C1 | 54.0 (2) |
Symmetry codes: (i) x, y, z+1; (ii) −x+3/2, y+1/2, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+2, −y+1, −z; (vi) −x+2, −y+2, −z; (vii) −x+3/2, y−1/2, −z−1/2; (viii) −x+3/2, y+1/2, −z−1/2; (ix) x−1/2, −y+3/2, z−1/2; (x) x+1/2, −y+3/2, z+1/2; (xi) x+1/2, −y+3/2, z−1/2; (xii) x, y, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—D22···O7iii | 1.12 (1) | 2.52 (1) | 3.429 (3) | 138 (1) |
C3—D31···O7ii | 1.10 (1) | 2.58 (1) | 3.544 (3) | 147 (1) |
C5—D52···O7xii | 1.09 (1) | 2.48 (1) | 3.538 (3) | 163 (1) |
C6—D62···O7iii | 1.12 (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, y−1/2, −z+1/2; (xii) x, y, z−1. |
Experimental details
Crystal data |
Chemical formula | C6D10O |
Mr | 108.14 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 5 |
a, b, c (Å) | 11.7105 (1), 7.1198 (1), 6.8621 (1) |
β (°) | 95.5627 (3) |
V (Å3) | 569.45 (1) |
Z | 4 |
Radiation type | Time-of-flight neutron, λ = 0.83-9.01 Å |
Specimen shape, size (mm) | Cylinder, 25 × 11 |
|
Data collection |
Diffractometer | HRPD diffractometer |
Specimen mounting | Standard cylindrical vanadium sample holder |
Data collection mode | ? |
Scan method | Tof 20-220 ms |
2θ values (°) | 2θmin = ? 2θmax = ? 2θstep = ? |
|
Refinement |
R factors and goodness of fit | Rp = 0.047, Rwp = 0.044, Rexp = 0.024, R(F2) = 0.04306, χ2 = 3.460 |
No. of data points | 17807 |
No. of parameters | 99 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—D22···O7i | 1.119 (3) | 2.515 (3) | 3.429 (3) | 138.0 (2) |
C3—D31···O7ii | 1.098 (4) | 2.575 (3) | 3.544 (3) | 146.6 (2) |
C5—D52···O7iii | 1.090 (3) | 2.481 (3) | 3.538 (3) | 162.9 (2) |
C6—D62···O7i | 1.123 (3) | 2.591 (3) | 3.473 (3) | 134.62 (18) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y, z−1. |
Experimental and calculated intra-molecular geometry (Å, 0) for CHO. topParameter | III 5 Ka | II 150 Kb | MM4c |
O7 C1 | 1.225 (3) | 1.221 (3) | 1.212 |
C1 C2 | 1.494 (3) | 1.511 (2) | 1.524 |
C1 C6 | 1.495 (3) | 1.523 (2) | |
C2 C3 | 1.526 (3) | 1.541 (3) | 1.542 |
C3 C4 | 1.543 (3) | 1.529 (3) | 1.536 |
C4 C5 | 1.517 (3) | 1.533 (3) | |
C5 C6 | 1.529 (3) | 1.542 (3) | |
<C C> | 1.517 (3) | 1.530 (3) | 1.534 |
<C H/D> | 1.102 (3) | 0.98 | 1.112 |
O7 C1 C2 | 122.5 (2) | 122.61 (15) | 122.4 |
O7 C1 C6 | 122.0 (2) | 121.93 (15) | |
C2 C1 C6 | 115.51 (17) | 115.45 (14) | 115.1 |
C1 C2 C3 | 111.84 (17) | 112.29 (15) | 110.8 |
C2 C3 C4 | 110.62 (16) | 111.63 (15) | 111.3 |
C3 C4 C5 | 110.07 (17) | 110.85 (16) | 110.8 |
C4 C5 C6 | 110.21 (17) | 111.04 (15) | |
C1 C6 C5 | 111.97 (17) | 111.65 (13) | |
O7 C1 C6 C5 | 131.6 (2) | 132.53 (17) | 130.9 |
O7 C1 C2 C3 | -132.3 (2) | -133.44 (17) | |
C6 C1 C2 C3 | 49.0 (2) | 47.68 (19) | 51.5 |
C2 C1 C6 C5 | -49.8 (2) | -48.58 (19) | |
C2 C3 C4 C5 | 58.5 (2) | 56.8 (2) | 57.3 |
C3 C4 C5 C6 | -58.9 (2) | -57.8 (2) | |
C4 C5 C6 C1 | 54.0 (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). |