The structure of 4-methylpyridine-N-oxide has been determined at 250, 100 and 10 K by combined synchrotron (C6H7NO) and neutron (C6D7NO) powder diffraction experiments. At 250 K the space group is I41/amd and the tetragonal unit cell [a = b = 7.941 (2), c = 19.600 (5) Å] contains eight equivalent molecules. At 100 K the structure is orthorhombic, with space group Fddd, a = 12.138 (2), b = 10.237 (2) and c = 19.568 (3) Å. The 16 equivalent molecules are rotated by about 8° around the c axis with respect to positions at high temperature. At 10 K the best structural model corresponds to a tetragonal unit cell with the space group P41, a = b = 15.410 (2) Å and c = 19.680 (3) Å. The 32 molecules (eight molecules in the asymmetric unit) show complex reorientations around the three cell axes. Whereas at 250 and 100 K the deuterated methyl groups are largely disordered, at 10 K they are ordered in-phase along infinite chains parallel to a and b. Face-to-face methyl groups along c are in an eclipsed configuration. The structure at 10 K suggests that the manifold of rotational tunnelling transitions could be due to inequivalent lattice sites for crystallographically independent methyl groups.
Supporting information
CCDC references: 618454; 618455; 618456
Fully deuterated sample was prepared by repeated exchanges with heavy water
For all compounds, program(s) used to refine structure: FULLPROF; molecular graphics: DIAMOND.
(250K) 4-methylpyridine-N-oxide
top
Crystal data top
C5D4NO·(CD3) | V = 1236.03 (6) Å3 |
Mr = 116 | Z = 8 |
Tetragonal, I41/amd | Melting point: 463 K |
Hall symbol: -I 4bd 2 | Constant Wavelength neutron radiation, λ = 1.225300 Å |
a = 7.9411 (2) Å | T = 250 K |
c = 19.6002 (5) Å | cylinder, ? × ? × ? mm |
Data collection top
Home made powder diffractometer | Specimen mounting: vanadium |
Radiation source: nuclear reactor, 3T2 | 2θmin = −0.026°, 2θmax = 125.424°, 2θstep = 0.050° |
Refinement top
Rp = 2.045 | Profile function: pseudo-voigt |
Rwp = 2.506 | 49 parameters |
Rexp = 1.501 | 0 restraints |
RBragg = 4.610 | |
χ2 = 2.789 | Background function: FullProf Background function number |
2279 data points | |
Crystal data top
C5D4NO·(CD3) | V = 1236.03 (6) Å3 |
Mr = 116 | Z = 8 |
Tetragonal, I41/amd | Constant Wavelength neutron radiation, λ = 1.225300 Å |
a = 7.9411 (2) Å | T = 250 K |
c = 19.6002 (5) Å | cylinder, ? × ? × ? mm |
Data collection top
Home made powder diffractometer | 2θmin = −0.026°, 2θmax = 125.424°, 2θstep = 0.050° |
Specimen mounting: vanadium | |
Refinement top
Rp = 2.045 | χ2 = 2.789 |
Rwp = 2.506 | 2279 data points |
Rexp = 1.501 | 49 parameters |
RBragg = 4.610 | 0 restraints |
Special details top
Geometry. Rigid body group non refined |
Refinement. Two rigid-body groups (C5D7NO and CD3 methyl group) with TLS |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
PI1 | 0.00000 | 0.25000 | 0.56339 | 0.00000 | |
PI2 | 0.00000 | 0.25000 | 0.49468 | 0.00000 | |
PI3 | 0.00000 | 0.10254 | 0.59687 | 0.00000 | 0.50000 |
PI4 | 0.00000 | 0.39746 | 0.59687 | 0.00000 | 0.50000 |
PI5 | 0.00000 | 0.10206 | 0.66836 | 0.00000 | 0.50000 |
PI6 | 0.00000 | 0.39794 | 0.66836 | 0.00000 | 0.50000 |
PI7 | 0.00000 | 0.25000 | 0.70584 | 0.00000 | |
PI8 | 0.00000 | 0.25000 | 0.78130 | 0.00000 | |
PI9 | 0.00000 | −0.00944 | 0.56656 | 0.00000 | 0.50000 |
PI10 | 0.00000 | 0.50944 | 0.56656 | 0.00000 | 0.50000 |
PI11 | 0.00000 | −0.02099 | 0.69313 | 0.00000 | 0.50000 |
PI12 | 0.00000 | 0.52099 | 0.69313 | 0.00000 | 0.50000 |
MI2 | 0.00000 | 0.14048 | 0.79950 | 0.00000 | 0.50000 |
MI3 | 0.09485 | 0.30476 | 0.79950 | 0.00000 | 0.25000 |
MI4 | −0.09485 | 0.30476 | 0.79950 | 0.00000 | 0.25000 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
PI1 | 0.01725 | 0.02145 | 0.00194 | 0.00000 | 0.00000 | 0.00000 |
PI2 | 0.02551 | 0.02663 | 0.00194 | 0.00000 | 0.00000 | 0.00000 |
PI3 | 0.02703 | 0.02007 | 0.00214 | 0.00000 | 0.00000 | −0.00036 |
PI4 | 0.02703 | 0.02007 | 0.00214 | 0.00000 | 0.00000 | 0.00036 |
PI5 | 0.02647 | 0.01967 | 0.00214 | 0.00000 | 0.00000 | 0.00022 |
PI6 | 0.02647 | 0.01967 | 0.00214 | 0.00000 | 0.00000 | −0.00022 |
PI7 | 0.01628 | 0.02084 | 0.00194 | 0.00000 | 0.00000 | 0.00000 |
PI8 | 0.02460 | 0.02607 | 0.00194 | 0.00000 | 0.00000 | 0.00000 |
PI9 | 0.05404 | 0.02128 | 0.00255 | 0.00000 | 0.00000 | −0.00107 |
PI10 | 0.05404 | 0.02128 | 0.00255 | 0.00000 | 0.00000 | 0.00107 |
PI11 | 0.05591 | 0.02034 | 0.00261 | 0.00000 | 0.00000 | 0.00078 |
PI12 | 0.05591 | 0.02034 | 0.00261 | 0.00000 | 0.00000 | −0.00078 |
MI2 | 0.19500 | 0.01947 | 0.00205 | 0.00000 | 0.00000 | 0.00008 |
MI3 | 0.05933 | 0.15515 | 0.00210 | −0.07833 | −0.00011 | −0.00004 |
MI4 | 0.05933 | 0.15515 | 0.00210 | 0.07833 | 0.00011 | −0.00004 |
Geometric parameters (Å, º) top
PI1—PI2 | 1.347 | PI5—PI6 | 1.479 |
PI1—PI3 | 1.342 | PI3—PI7 | 1.070 |
PI3—PI4 | 1.401 | PI4—PI8 | 1.090 |
PI4—PI5 | 1.386 | PI6—MI2 | 0.940 |
| | | |
PI3—PI1—PI3 | 121.5 | PI4—PI5—PI4 | 116.0 |
PI1—PI3—PI4 | 119.4 | PI1—PI3—PI7 | 117.0 |
PI3—PI4—PI5 | 122.9 | PI3—PI4—PI8 | 116.6 |
PI4—PI5—PI6 | 122.2 | PI5—PI6—MI2 | 112.3 |
(100K) 4-methylpyridine-N-oxide
top
Crystal data top
C5D4NO·(CD3) | V = 2431.36 (8) Å3 |
Mr = 116 | Z = 16 |
Orthorhombic, FDDD | Melting point: 463 K |
Hall symbol: -F 2uv 2vw | Constant Wavelength Neutron radiation, λ = 1.225300 Å |
a = 12.1382 (3) Å | T = 100 K |
b = 10.2367 (2) Å | cylinder, ? × ? × ? mm |
c = 19.5676 (3) Å | |
Data collection top
Home made powder diffractometer | Specimen mounting: vanadium |
Radiation source: nuclear reactor, 3T2 | 2θmin = −0.043°, 2θmax = 125.407°, 2θstep = 0.050° |
Refinement top
Rp = 2.246 | Profile function: pseudo-voigt |
Rwp = 2.750 | 63 parameters |
Rexp = 1.419 | 0 restraints |
RBragg = 4.201 | |
χ2 = 3.725 | Background function: FullProf Background function number |
2079 data points | |
Crystal data top
C5D4NO·(CD3) | V = 2431.36 (8) Å3 |
Mr = 116 | Z = 16 |
Orthorhombic, FDDD | Constant Wavelength Neutron radiation, λ = 1.225300 Å |
a = 12.1382 (3) Å | T = 100 K |
b = 10.2367 (2) Å | cylinder, ? × ? × ? mm |
c = 19.5676 (3) Å | |
Data collection top
Home made powder diffractometer | 2θmin = −0.043°, 2θmax = 125.407°, 2θstep = 0.050° |
Specimen mounting: vanadium | |
Refinement top
Rp = 2.246 | χ2 = 3.725 |
Rwp = 2.750 | 2079 data points |
Rexp = 1.419 | 63 parameters |
RBragg = 4.201 | 0 restraints |
Special details top
Geometry. Rigid body group non refined |
Refinement. Two rigid-body groups (C5D7NO and CD3 methyl group) with TLS |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
PN1 | 0.62500 | 0.12500 | 0.31363 | 0.00000 | |
PN2 | 0.62500 | 0.12500 | 0.24481 | 0.00000 | |
PN3 | 0.54847 | 0.19307 | 0.34637 | 0.00000 | 0.50000 |
PN4 | 0.70153 | 0.05693 | 0.34638 | 0.00000 | 0.50000 |
PN5 | 0.54711 | 0.19428 | 0.41813 | 0.00000 | 0.50000 |
PN6 | 0.70289 | 0.05572 | 0.41813 | 0.00000 | 0.50000 |
PN7 | 0.62500 | 0.12500 | 0.45632 | 0.00000 | |
PN8 | 0.62500 | 0.12500 | 0.53190 | 0.00000 | |
PN9 | 0.48973 | 0.24531 | 0.31619 | 0.00000 | 0.50000 |
PN10 | 0.76027 | 0.00469 | 0.31620 | 0.00000 | 0.50000 |
PN11 | 0.48314 | 0.25118 | 0.44354 | 0.00000 | 0.50000 |
PN12 | 0.76686 | −0.00118 | 0.44354 | 0.00000 | 0.50000 |
MN2 | 0.61868 | 0.21289 | 0.55022 | 0.00000 | 0.50000 |
MN3 | 0.56398 | 0.07456 | 0.55022 | 0.00000 | 0.50000 |
MN4 | 0.69235 | 0.08754 | 0.55022 | 0.00000 | 0.50000 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
PN1 | 0.00408 | 0.00513 | 0.00074 | 0.00011 | 0.00000 | 0.00000 |
PN2 | 0.00450 | 0.00785 | 0.00074 | −0.00081 | 0.00000 | 0.00000 |
PN3 | 0.00493 | 0.00680 | 0.00092 | 0.00176 | 0.00009 | 0.00039 |
PN4 | 0.00493 | 0.00680 | 0.00092 | 0.00176 | −0.00009 | −0.00039 |
PN5 | 0.00493 | 0.00665 | 0.00093 | 0.00144 | 0.00028 | −0.00004 |
PN6 | 0.00493 | 0.00665 | 0.00093 | 0.00144 | −0.00028 | 0.00004 |
PN7 | 0.00403 | 0.00479 | 0.00074 | −0.00070 | 0.00000 | 0.00000 |
PN8 | 0.00445 | 0.00752 | 0.00074 | −0.00262 | 0.00000 | 0.00000 |
PN9 | 0.00706 | 0.01251 | 0.00131 | 0.00485 | 0.00003 | 0.00101 |
PN10 | 0.00706 | 0.01251 | 0.00131 | 0.00485 | −0.00003 | −0.00101 |
PN11 | 0.00727 | 0.01273 | 0.00137 | 0.00471 | 0.00062 | −0.00034 |
PN12 | 0.00727 | 0.01273 | 0.00137 | 0.00471 | −0.00062 | 0.00034 |
MN2 | 0.06011 | 0.00467 | 0.00085 | 0.00578 | 0.00003 | −0.00007 |
MN3 | 0.02244 | 0.05765 | 0.00073 | −0.03138 | −0.00001 | 0.00000 |
MN4 | 0.01414 | 0.06932 | 0.00082 | 0.02591 | −0.00002 | 0.00006 |
Geometric parameters (Å, º) top
PI1—PI2 | 1.347 | PI5—PI6 | 1.479 |
PI1—PI3 | 1.342 | PI3—PI7 | 1.070 |
PI3—PI4 | 1.401 | PI4—PI8 | 1.090 |
PI4—PI5 | 1.386 | PI6—MI2 | 0.980 |
| | | |
PI3—PI1—PI3 | 121.5 | PI4—PI5—PI4 | 116.0 |
PI1—PI3—PI4 | 119.4 | PI1—PI3—PI7 | 117.0 |
PI3—PI4—PI5 | 122.9 | PI3—PI4—PI8 | 116.6 |
PI4—PI5—PI6 | 122.2 | PI5—PI6—MI2 | 112.9 |
(10K) 4-methylpyridine-N-oxide
top
Crystal data top
C5D4NO·(CD3) | V = 4673.61 (10) Å3 |
Mr = 116 | Z = 32 |
Tetragonal, P41 | Melting point: 463 K |
Hall symbol: P 4w | Constant Wavelength Neutron Diffraction radiation, λ = 1.225300 Å |
a = 15.41038 (19) Å | T = 10 K |
c = 19.6800 (3) Å | cylinder, ? × ? × ? mm |
Data collection top
Laboratoire Leon Brillouin diffractometer | Specimen mounting: vanadium |
Radiation source: nuclear reactor, 3T2 | 2θmin = −0.062°, 2θmax = 125.388°, 2θstep = 0.050° |
Refinement top
Rp = 2.797 | Profile function: pseudo-voigt |
Rwp = 3.365 | 36 parameters |
Rexp = 1.428 | 0 restraints |
RBragg = 4.047 | |
χ2 = 5.523 | Background function: FullProf Background function number |
2079 data points | |
Crystal data top
C5D4NO·(CD3) | V = 4673.61 (10) Å3 |
Mr = 116 | Z = 32 |
Tetragonal, P41 | Constant Wavelength Neutron Diffraction radiation, λ = 1.225300 Å |
a = 15.41038 (19) Å | T = 10 K |
c = 19.6800 (3) Å | cylinder, ? × ? × ? mm |
Data collection top
Laboratoire Leon Brillouin diffractometer | 2θmin = −0.062°, 2θmax = 125.388°, 2θstep = 0.050° |
Specimen mounting: vanadium | |
Refinement top
Rp = 2.797 | χ2 = 5.523 |
Rwp = 3.365 | 2079 data points |
Rexp = 1.428 | 36 parameters |
RBragg = 4.047 | 0 restraints |
Special details top
Geometry. Rigid body group non refined |
Refinement. 16 rigid-body groups (C5D7NO and CD3) with isotropic Bs & TLS |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
PI1 | 0.65709 | 0.84503 | 0.56893 | 0.00441* | |
PI2 | 0.66059 | 0.85044 | 0.50069 | 0.00588* | |
PI3 | 0.68840 | 0.77401 | 0.59990 | 0.00224* | |
PI4 | 0.62237 | 0.91077 | 0.60447 | 0.00224* | |
PI5 | 0.68487 | 0.76816 | 0.67090 | 0.00224* | |
PI6 | 0.61863 | 0.90537 | 0.67549 | 0.00224* | |
PI7 | 0.64984 | 0.83381 | 0.71042 | 0.00224* | |
PI8 | 0.64600 | 0.82787 | 0.78536 | 0.01103* | |
PI9 | 0.71501 | 0.72447 | 0.56805 | 0.01445* | |
PI10 | 0.59885 | 0.96508 | 0.57610 | 0.01445* | |
PI11 | 0.71116 | 0.70915 | 0.69359 | 0.01445* | |
PI12 | 0.58982 | 0.96047 | 0.70200 | 0.01445* | |
MI2 | 0.61945 | 0.88463 | 0.80743 | 0.00000 | |
MI3 | 0.60720 | 0.77515 | 0.80172 | 0.00000 | |
MI4 | 0.70827 | 0.81906 | 0.80703 | 0.00000 | |
PJ1 | 0.91012 | 0.59303 | 0.06510 | 0.00441* | |
PJ2 | 0.91653 | 0.58600 | −0.00292 | 0.00588* | |
PJ3 | 0.88430 | 0.52406 | 0.10153 | 0.00224* | |
PJ4 | 0.92969 | 0.66886 | 0.09497 | 0.00224* | |
PJ5 | 0.87756 | 0.53115 | 0.17232 | 0.00224* | |
PJ6 | 0.92310 | 0.67642 | 0.16574 | 0.00224* | |
PJ7 | 0.89683 | 0.60762 | 0.20614 | 0.00224* | |
PJ8 | 0.88979 | 0.61535 | 0.28084 | 0.01103* | |
PJ9 | 0.86990 | 0.46598 | 0.07401 | 0.01445* | |
PJ10 | 0.94975 | 0.72074 | 0.06247 | 0.01445* | |
PJ11 | 0.85631 | 0.47327 | 0.19958 | 0.01445* | |
PJ12 | 0.93972 | 0.73937 | 0.18753 | 0.01445* | |
MJ2 | 0.86939 | 0.55653 | 0.30360 | 0.00000 | |
MJ3 | 0.94984 | 0.63213 | 0.30345 | 0.00000 | |
MJ4 | 0.84451 | 0.66357 | 0.29537 | 0.00000 | |
PK1 | 0.91210 | 0.84290 | 0.32425 | 0.00441* | |
PK2 | 0.91424 | 0.83679 | 0.25601 | 0.00588* | |
PK3 | 0.83520 | 0.84164 | 0.35628 | 0.00224* | |
PK4 | 0.98691 | 0.85011 | 0.35873 | 0.00224* | |
PK5 | 0.83273 | 0.84799 | 0.42728 | 0.00224* | |
PK6 | 0.98493 | 0.85648 | 0.42974 | 0.00224* | |
PK7 | 0.90766 | 0.85557 | 0.46574 | 0.00224* | |
PK8 | 0.90531 | 0.86228 | 0.54068 | 0.01103* | |
PK9 | 0.77855 | 0.83573 | 0.32524 | 0.01445* | |
PK10 | 1.04546 | 0.85063 | 0.32955 | 0.01445* | |
PK11 | 0.76866 | 0.84666 | 0.45086 | 0.01445* | |
PK12 | 1.04745 | 0.86222 | 0.45537 | 0.01445* | |
MK2 | 0.89872 | 0.80076 | 0.56407 | 0.00000 | |
MK3 | 0.96261 | 0.89067 | 0.56036 | 0.00000 | |
MK4 | 0.85273 | 0.90079 | 0.55769 | 0.00000 | |
PL1 | 0.90415 | 0.84708 | 0.93959 | 0.00441* | |
PL2 | 0.90530 | 0.84062 | 1.00782 | 0.00588* | |
PL3 | 0.91160 | 0.77488 | 0.90188 | 0.00224* | |
PL4 | 0.89557 | 0.92558 | 0.91079 | 0.00224* | |
PL5 | 0.91042 | 0.78135 | 0.83086 | 0.00224* | |
PL6 | 0.89434 | 0.93255 | 0.83980 | 0.00224* | |
PL7 | 0.90174 | 0.86047 | 0.79811 | 0.00224* | |
PL8 | 0.90047 | 0.86756 | 0.72317 | 0.01103* | |
PL9 | 0.91819 | 0.71481 | 0.92860 | 0.01445* | |
PL10 | 0.88999 | 0.97995 | 0.94428 | 0.01445* | |
PL11 | 0.91669 | 0.72081 | 0.80254 | 0.01445* | |
PL12 | 0.88723 | 0.99775 | 0.81892 | 0.01445* | |
ML2 | 0.89789 | 0.80594 | 0.69948 | 0.00000 | |
ML3 | 0.84609 | 0.90311 | 0.70566 | 0.00000 | |
ML4 | 0.95641 | 0.89934 | 0.70429 | 0.00000 | |
PM1 | 0.65259 | 0.58745 | 0.44163 | 0.00441* | |
PM2 | 0.65923 | 0.58914 | 0.50984 | 0.00588* | |
PM3 | 0.64893 | 0.51065 | 0.40957 | 0.00224* | |
PM4 | 0.64977 | 0.66260 | 0.40720 | 0.00224* | |
PM5 | 0.64202 | 0.50864 | 0.33858 | 0.00224* | |
PM6 | 0.64286 | 0.66108 | 0.33622 | 0.00224* | |
PM7 | 0.63882 | 0.58394 | 0.30019 | 0.00224* | |
PM8 | 0.63152 | 0.58208 | 0.22527 | 0.01103* | |
PM9 | 0.65154 | 0.45371 | 0.44056 | 0.01445* | |
PM10 | 0.65302 | 0.72103 | 0.43640 | 0.01445* | |
PM11 | 0.63927 | 0.44464 | 0.31498 | 0.01445* | |
PM12 | 0.64082 | 0.72387 | 0.31064 | 0.01445* | |
MM2 | 0.59136 | 0.53072 | 0.20831 | 0.00000 | |
MM3 | 0.60469 | 0.64026 | 0.20584 | 0.00000 | |
MM4 | 0.69266 | 0.57378 | 0.20160 | 0.00000 | |
PN1 | 0.66532 | 0.84687 | 0.19799 | 0.00441* | |
PN2 | 0.66450 | 0.85046 | 0.26636 | 0.00588* | |
PN3 | 0.73555 | 0.81521 | 0.16615 | 0.00224* | |
PN4 | 0.59589 | 0.87503 | 0.16320 | 0.00224* | |
PN5 | 0.73664 | 0.81138 | 0.09502 | 0.00224* | |
PN6 | 0.59652 | 0.87139 | 0.09205 | 0.00224* | |
PN7 | 0.66702 | 0.83942 | 0.05624 | 0.00224* | |
PN8 | 0.66793 | 0.83548 | −0.01884 | 0.01103* | |
PN9 | 0.78822 | 0.79409 | 0.19744 | 0.01445* | |
PN10 | 0.54250 | 0.89932 | 0.19224 | 0.01445* | |
PN11 | 0.79520 | 0.78513 | 0.07161 | 0.01445* | |
PN12 | 0.53855 | 0.89504 | 0.06617 | 0.01445* | |
MN2 | 0.71334 | 0.87937 | −0.04002 | 0.00000 | |
MN3 | 0.68452 | 0.77288 | −0.03680 | 0.00000 | |
MN4 | 0.60664 | 0.85103 | −0.03989 | 0.00000 | |
PO1 | 0.59572 | 0.09011 | 0.45173 | 0.00441* | |
PO2 | 0.58956 | 0.08190 | 0.51968 | 0.00588* | |
PO3 | 0.63162 | 0.02574 | 0.41537 | 0.00224* | |
PO4 | 0.56583 | 0.16249 | 0.42185 | 0.00224* | |
PO5 | 0.63815 | 0.03407 | 0.34465 | 0.00224* | |
PO6 | 0.57214 | 0.17127 | 0.35115 | 0.00224* | |
PO7 | 0.60851 | 0.10715 | 0.31083 | 0.00224* | |
PO8 | 0.61528 | 0.11618 | 0.23620 | 0.01103* | |
PO9 | 0.65388 | −0.02980 | 0.44289 | 0.01445* | |
PO10 | 0.53813 | 0.21079 | 0.45429 | 0.01445* | |
PO11 | 0.66782 | −0.02002 | 0.31745 | 0.01445* | |
PO12 | 0.54692 | 0.23128 | 0.32936 | 0.01445* | |
MO2 | 0.55502 | 0.13274 | 0.21386 | 0.00000 | |
MO3 | 0.66005 | 0.16508 | 0.22210 | 0.00000 | |
MO4 | 0.63620 | 0.05794 | 0.21283 | 0.00000 | |
PP1 | 0.65503 | 0.59892 | 0.82756 | 0.00441* | |
PP2 | 0.66032 | 0.59750 | 0.75927 | 0.00588* | |
PP3 | 0.57676 | 0.60449 | 0.85719 | 0.00224* | |
PP4 | 0.72814 | 0.59472 | 0.86450 | 0.00224* | |
PP5 | 0.57100 | 0.60598 | 0.92824 | 0.00224* | |
PP6 | 0.72288 | 0.59618 | 0.93558 | 0.00224* | |
PP7 | 0.64405 | 0.60185 | 0.96916 | 0.00224* | |
PP8 | 0.63824 | 0.60341 | 1.04416 | 0.01103* | |
PP9 | 0.52162 | 0.60758 | 0.82428 | 0.01445* | |
PP10 | 0.78794 | 0.59039 | 0.83715 | 0.01445* | |
PP11 | 0.50594 | 0.61057 | 0.94980 | 0.01445* | |
PP12 | 0.78412 | 0.59261 | 0.96325 | 0.01445* | |
MP2 | 0.70022 | 0.60778 | 1.06718 | 0.00000 | |
MP3 | 0.60160 | 0.65694 | 1.06187 | 0.00000 | |
MP4 | 0.60833 | 0.54677 | 1.06359 | 0.00000 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
MI2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MI3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MI4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
MJ2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MJ3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MJ4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
MK2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MK3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MK4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
ML2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
ML3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
ML4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
MM2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MM3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MM4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
MN2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MN3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MN4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
MO2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MO3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MO4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
MP2 | 0.01211 | 0.00142 | 0.00005 | 0.00323 | −0.00001 | 0.00002 |
MP3 | 0.01003 | 0.00257 | 0.00005 | −0.00369 | −0.00001 | −0.00002 |
MP4 | 0.00472 | 0.00884 | 0.00005 | 0.00047 | 0.00002 | 0.00000 |
Geometric parameters (Å, º) top
PI1—PI2 | 1.347 | PI5—PI6 | 1.479 |
PI1—PI3 | 1.342 | PI3—PI7 | 1.070 |
PI3—PI4 | 1.401 | PI4—PI8 | 1.090 |
PI4—PI5 | 1.386 | PI6—MI2 | 1.070 |
| | | |
PI3—PI1—PI3 | 121.5 | PI4—PI5—PI4 | 116.0 |
PI1—PI3—PI4 | 119.4 | PI1—PI3—PI7 | 117.0 |
PI3—PI4—PI5 | 122.9 | PI3—PI4—PI8 | 116.6 |
PI4—PI5—PI6 | 122.2 | PI5—PI6—MI2 | 113.0 |
Experimental details
| (250K) | (100K) | (10K) |
Crystal data |
Chemical formula | C5D4NO·(CD3) | C5D4NO·(CD3) | C5D4NO·(CD3) |
Mr | 116 | 116 | 116 |
Crystal system, space group | Tetragonal, I41/amd | Orthorhombic, FDDD | Tetragonal, P41 |
Temperature (K) | 250 | 100 | 10 |
a, b, c (Å) | 7.9411 (2), 7.9411 (2), 19.6002 (5) | 12.1382 (3), 10.2367 (2), 19.5676 (3) | 15.41038 (19), 15.41038 (19), 19.6800 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 1236.03 (6) | 2431.36 (8) | 4673.61 (10) |
Z | 8 | 16 | 32 |
Radiation type | Constant Wavelength neutron, λ = 1.225300 Å | Constant Wavelength Neutron, λ = 1.225300 Å | Constant Wavelength Neutron Diffraction, λ = 1.225300 Å |
Specimen shape, size (mm) | Cylinder, ? × ? × ? | Cylinder, ? × ? × ? | Cylinder, ? × ? × ? |
|
Data collection |
Diffractometer | Home made powder diffractometer | Home made powder diffractometer | Laboratoire Leon Brillouin |
Specimen mounting | Vanadium | Vanadium | Vanadium |
Data collection mode | ? | ? | ? |
Scan method | ? | ? | ? |
2θ values (°) | 2θmin = −0.026 2θmax = 125.424 2θstep = 0.050 | 2θmin = −0.043 2θmax = 125.407 2θstep = 0.050 | 2θmin = −0.062 2θmax = 125.388 2θstep = 0.050 |
|
Refinement |
R factors and goodness of fit | Rp = 2.045, Rwp = 2.506, Rexp = 1.501, RBragg = 4.610, χ2 = 2.789 | Rp = 2.246, Rwp = 2.750, Rexp = 1.419, RBragg = 4.201, χ2 = 3.725 | Rp = 2.797, Rwp = 3.365, Rexp = 1.428, RBragg = 4.047, χ2 = 5.523 |
No. of data points | 2279 | 2079 | 2079 |
No. of parameters | 49 | 63 | 36 |
Selected geometric parameters (Å, º) for (250K) topPI1—PI2 | 1.347 | PI5—PI6 | 1.479 |
PI1—PI3 | 1.342 | PI3—PI7 | 1.070 |
PI3—PI4 | 1.401 | PI4—PI8 | 1.090 |
PI4—PI5 | 1.386 | PI6—MI2 | 0.940 |
| | | |
PI3—PI1—PI3 | 121.5 | PI4—PI5—PI4 | 116.0 |
PI1—PI3—PI4 | 119.4 | PI1—PI3—PI7 | 117.0 |
PI3—PI4—PI5 | 122.9 | PI3—PI4—PI8 | 116.6 |
PI4—PI5—PI6 | 122.2 | PI5—PI6—MI2 | 112.3 |
Selected geometric parameters (Å, º) for (100K) topPI1—PI2 | 1.347 | PI5—PI6 | 1.479 |
PI1—PI3 | 1.342 | PI3—PI7 | 1.070 |
PI3—PI4 | 1.401 | PI4—PI8 | 1.090 |
PI4—PI5 | 1.386 | PI6—MI2 | 0.980 |
| | | |
PI3—PI1—PI3 | 121.5 | PI4—PI5—PI4 | 116.0 |
PI1—PI3—PI4 | 119.4 | PI1—PI3—PI7 | 117.0 |
PI3—PI4—PI5 | 122.9 | PI3—PI4—PI8 | 116.6 |
PI4—PI5—PI6 | 122.2 | PI5—PI6—MI2 | 112.9 |
Selected geometric parameters (Å, º) for (10K) topPI1—PI2 | 1.347 | PI5—PI6 | 1.479 |
PI1—PI3 | 1.342 | PI3—PI7 | 1.070 |
PI3—PI4 | 1.401 | PI4—PI8 | 1.090 |
PI4—PI5 | 1.386 | PI6—MI2 | 1.070 |
| | | |
PI3—PI1—PI3 | 121.5 | PI4—PI5—PI4 | 116.0 |
PI1—PI3—PI4 | 119.4 | PI1—PI3—PI7 | 117.0 |
PI3—PI4—PI5 | 122.9 | PI3—PI4—PI8 | 116.6 |
PI4—PI5—PI6 | 122.2 | PI5—PI6—MI2 | 113.0 |