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The crystal structure of perdeuterated methanol hemiammoniate, CD3OD·0.5ND3, has been solved from neutron powder diffraction data collected at 4.2 and 180 K. The structure is orthorhombic, space group Pn21a (Z = 4), with unit-cell dimensions a = 12.70615 (16), b = 8.84589 (9), c = 4.73876 (4) Å, V = 532.623 (8) Å3 [ρcalc = 1149.57 (2) kg m−3] at 4.2 K, and a = 12.90413 (16), b = 8.96975 (8), c = 4.79198 (4) Å, V = 554.656 (7) Å3 [ρcalc = 1103.90 (1) kg m−3] at 180 K. The crystal structure was determined by ab initio methods from the powder data; atomic coordinates and isotropic displacement parameters were subsequently refined by the Rietveld method to Rp ≃ 2% at both temperatures. The crystal structure comprises a three-dimensionally hydrogen-bonded network in which the ND3 molecules are tetrahedrally coordinated by the hydroxy moieties of the methanol molecule. This connectivity leads to the formation of zigzag chains of ammonia–hydroxy groups extending along the c axis, formed via N—D···O hydrogen bonds; these chains are cross-linked along the a axis through the hydroxy moiety of the second methanol molecule via N—D···O and O—D···O hydrogen bonds. This `bridging' hydroxy group in turn donates an O—D···N hydrogen bond to ammonia in adjacent chains stacked along the b axis. The methyl deuterons in methanol hemiammoniate, unlike those in methanol monoammoniate, do not participate in hydrogen bonding and reveal evidence of orientational disorder at 180 K. The relative volume change on warming from 4.2 to 180 K, ΔV/V, is + 4.14%, which is comparable to, but more nearly isotropic (as determined from the relative change in axial lengths, e.g. Δa/a) than, that observed in deuterated methanol monohydrate, and very similar to what is observed in methanol monoammoniate.
Supporting information
| Crystallographic Information File (CIF) https://doi.org/10.1107/S0021889810005595/db5076sup1.cif Contains datablocks METHANOL_HEMIAMMONIA_publ, METHANOL_HEMIAMMONIA_overall, METHANOL_HEMIAMMONIA_phase_1, METHANOL_HEMIAMMONIA_phase_2, METHANOL_HEMIAMMONIA_p_03, METHANOL_HEMIAMMONIA_p_04, METHANOL_HEMIAMMONIA_p_05, METHANOL_HEMIAMMONIA_publ_180, METHANOL_HEMIAMMONIA_overall_180, METHANOL_HEMIAMMONIA_phase_1_180, METHANOL_HEMIAMMONIA_phase_2_180, METHANOL_HEMIAMMONIA_p_02_180, METHANOL_HEMIAMMONIA_p_03_180, METHANOL_HEMIAMMONIA_p_04_180, METHANOL_HEMIAMMONIA_p_05_180, METHANOL_HEMIAMMONIA_p_07_180 |
| Portable Document Format (PDF) file https://doi.org/10.1107/S0021889810005595/db5076sup2.pdf Unit-cell indexing |
CCDC references: 775216; 775217
(METHANOL_HEMIAMMONIA_phase_1)
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Crystal data top
CD7NO | c = 7.5847 (3) Å |
Mr = 56.11 | V = 640.88 (3) Å3 |
Orthorhombic, Pbca | Z = 8 |
a = 11.0386 (4) Å | ? radiation, λ = ? Å |
b = 7.6547 (3) Å | ?; ?; ?, ?; ?; ? × ?; ?; ? mm |
Refinement top
Least-squares matrix: full | 4404 data points |
Rp = 0.023 | Profile function: TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024093 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 2602.6 #6 (sig-2) = 106.7
#7 (gam-0) = 0.00 #8 (gam-1) = 0.00 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0, TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024093 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 2284.4 #6 (sig-2) = 78.2
#7 (gam-0) = 0.00 #8 (gam-1) = 33.26 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0 |
Rwp = 0.027 | 5 parameters |
Rexp = 0.009 | 22 restraints |
R(F2) = 0.05592 | (Δ/σ)max < 0.001 |
χ2 = 54.317 | Background function: GSAS Background function number 1 with 15 terms.
Shifted Chebyshev function of 1st kind
1: 5.47986 2: -0.604934 3: -9.454000E-02 4: 3.727370E-02
5: -0.254440 6: 0.150723 7: -7.130570E-02 8: -2.600680E-02
9: -6.342830E-0210: -5.013720E-0211: 2.116950E-0212: -6.323090E-03
13: -1.822140E-0214: 2.743080E-0215: -5.135170E-02 |
Crystal data top
CD7NO | c = 7.5847 (3) Å |
Mr = 56.11 | V = 640.88 (3) Å3 |
Orthorhombic, Pbca | Z = 8 |
a = 11.0386 (4) Å | ? radiation, λ = ? Å |
b = 7.6547 (3) Å | ?; ?; ?, ?; ?; ? × ?; ?; ? mm |
Refinement top
Rp = 0.023 | χ2 = 54.317 |
Rwp = 0.027 | 4404 data points |
Rexp = 0.009 | 5 parameters |
R(F2) = 0.05592 | 22 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C | 0.26307 | 0.04606 | 0.21694 | 0.01067 | |
O | 0.13628 | 0.01387 | 0.23358 | 0.009 | |
D1 | 0.28569 | 0.17895 | 0.25136 | 0.03333 | |
D2 | 0.29373 | 0.01828 | 0.08409 | 0.03933 | |
D3 | 0.31134 | −0.04138 | 0.2996 | 0.03233 | |
D4 | 0.09104 | 0.09952 | 0.15652 | 0.01733 | |
N | 0.49051 | 0.74662 | 1.02666 | 0.00967 | |
D5 | 0.54064 | 0.82819 | 1.10533 | 0.02333 | |
D6 | 0.44258 | 0.8252 | 0.94656 | 0.02267 | |
D7 | 0.54772 | 0.6783 | 0.95125 | 0.023 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C | 0.009 | 0.007 | 0.016 | 0.002 | 0.002 | −0.001 |
O | 0.008 | 0.006 | 0.013 | 0.002 | −0.002 | 0.001 |
D1 | 0.02 | 0.024 | 0.056 | −0.008 | 0.003 | −0.012 |
D2 | 0.023 | 0.077 | 0.018 | −0.004 | 0.011 | −0.005 |
D3 | 0.016 | 0.034 | 0.047 | 0.002 | −0.006 | 0.02 |
D4 | 0.02 | 0.019 | 0.013 | 0.001 | −0.001 | 0.004 |
N | 0.009 | 0.011 | 0.009 | 0.007 | −0.001 | 0.001 |
D5 | 0.026 | 0.024 | 0.02 | −0.005 | −0.003 | −0.008 |
D6 | 0.027 | 0.023 | 0.018 | −0.002 | −0.005 | 0.004 |
D7 | 0.023 | 0.018 | 0.028 | 0.006 | 0.0 | −0.002 |
Geometric parameters (Å, º) top
C—O | 1.4267 (1) | D3—D2 | 1.7083 (1) |
C—D1 | 1.0795 (1) | D4—C | 1.9959 (1) |
C—D2 | 1.0840 (1) | D4—O | 1.0104 (1) |
C—D3 | 1.0607 (1) | D4—Ni | 1.7460 (1) |
C—D4 | 1.9959 (1) | N—D4ii | 1.7460 (1) |
O—C | 1.4267 (1) | N—D5 | 1.0257 (1) |
O—D3 | 2.0406 (1) | N—D6 | 1.0054 (1) |
O—D4 | 1.0104 (1) | N—D7 | 0.9997 (1) |
D1—C | 1.0795 (1) | D5—N | 1.0257 (1) |
D1—D2 | 1.7692 (1) | D5—D6 | 1.6194 (1) |
D1—D3 | 1.7489 (1) | D5—D7 | 1.6396 (1) |
D2—C | 1.0840 (1) | D6—N | 1.0054 (1) |
D2—D1 | 1.7692 (1) | D6—D5 | 1.6194 (1) |
D2—D3 | 1.7083 (1) | D6—D7 | 1.6164 (1) |
D3—C | 1.0607 (1) | D7—N | 0.9997 (1) |
D3—O | 2.0406 (1) | D7—D5 | 1.6396 (1) |
D3—D1 | 1.7489 (1) | D7—D6 | 1.6164 (1) |
| | | |
O—C—D1 | 111.6090 (2) | D2—C—D3 | 105.593 (2) |
O—C—D2 | 110.7707 (7) | C—O—D4 | 108.7611 (16) |
O—C—D3 | 109.3621 (16) | D5—N—D6 | 105.737 (3) |
D1—C—D2 | 109.7211 (6) | D5—N—D7 | 108.087 (2) |
D1—C—D3 | 109.604 (2) | D6—N—D7 | 107.438 (3) |
Symmetry codes: (i) −x+1/2, y−1/2, z−1; (ii) −x+1/2, y+1/2, z+1. |
(METHANOL_HEMIAMMONIA_phase_2)
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Crystal data top
C2D11NO2 | c = 4.73876 (4) Å |
Mr = 92.18 | V = 532.62 (1) Å3 |
Orthorhombic, Pn21a | Z = 4 |
a = 12.70615 (16) Å | ? radiation, λ = ? Å |
b = 8.84589 (9) Å | ?; ?; ?, ?; ?; ? × ?; ?; ? mm |
Refinement top
Least-squares matrix: full | 4404 data points |
Rp = 0.023 | Profile function: TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024093 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 2602.6 #6 (sig-2) = 106.7
#7 (gam-0) = 0.00 #8 (gam-1) = 0.00 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0, TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024093 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 2284.4 #6 (sig-2) = 78.2
#7 (gam-0) = 0.00 #8 (gam-1) = 33.26 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0 |
Rwp = 0.027 | 5 parameters |
Rexp = 0.009 | 22 restraints |
R(F2) = 0.05592 | (Δ/σ)max < 0.001 |
χ2 = 54.317 | Background function: GSAS Background function number 1 with 15 terms.
Shifted Chebyshev function of 1st kind
1: 5.47986 2: -0.604934 3: -9.454000E-02 4: 3.727370E-02
5: -0.254440 6: 0.150723 7: -7.130570E-02 8: -2.600680E-02
9: -6.342830E-0210: -5.013720E-0211: 2.116950E-0212: -6.323090E-03
13: -1.822140E-0214: 2.743080E-0215: -5.135170E-02 |
Crystal data top
C2D11NO2 | c = 4.73876 (4) Å |
Mr = 92.18 | V = 532.62 (1) Å3 |
Orthorhombic, Pn21a | Z = 4 |
a = 12.70615 (16) Å | ? radiation, λ = ? Å |
b = 8.84589 (9) Å | ?; ?; ?, ?; ?; ? × ?; ?; ? mm |
Refinement top
Rp = 0.023 | χ2 = 54.317 |
Rwp = 0.027 | 4404 data points |
Rexp = 0.009 | 5 parameters |
R(F2) = 0.05592 | 22 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.54422 | 0.2265 | 0.05788 | 0.00721* | |
O1 | 0.56931 | 0.22879 | 0.34733 | 0.00594* | |
D1 | 0.56403 | 0.33473 | −0.04779 | 0.03087* | |
D2 | 0.46046 | 0.20635 | 0.02671 | 0.03741* | |
D3 | 0.58601 | 0.13177 | −0.0443 | 0.02949* | |
D4 | 0.58619 | 0.34168 | 0.40422 | 0.01039* | |
N1 | 0.61428 | 0.52341 | 0.46339 | 0.00378* | |
D5 | 0.65748 | 0.53838 | 0.64563 | 0.0164* | |
D6 | 0.55199 | 0.59727 | 0.48765 | 0.01603* | |
D7 | 0.65814 | 0.55554 | 0.30293 | 0.01943* | |
C2 | 0.18865 | 0.90166 | 0.02951 | 0.00264* | |
O2 | 0.23586 | 1.04731 | 0.02785 | 0.00803* | |
D8 | 0.10738 | 0.90055 | −0.02161 | 0.03038* | |
D9 | 0.20057 | 0.84732 | 0.2342 | 0.02986* | |
D10 | 0.23088 | 0.8297 | −0.1249 | 0.03082* | |
D11 | 0.17797 | 1.11997 | 0.0717 | 0.01393* | |
Geometric parameters (Å, º) top
C1—O1 | 1.4083 (1) | D5—O2ii | 2.0584 (1) |
C1—D1 | 1.1093 (1) | D6—N1 | 1.0327 (1) |
C1—D2 | 1.0891 (1) | D6—D5 | 1.6213 (1) |
C1—D3 | 1.1040 (1) | D6—D7 | 1.6497 (1) |
C1—D4 | 2.0040 (1) | D7—N1 | 0.9846 (1) |
O1—C1 | 1.4083 (1) | D7—D5 | 1.6311 (1) |
O1—D2 | 2.0641 (1) | D7—D6 | 1.6497 (1) |
O1—D3 | 2.0557 (1) | D7—O2iii | 2.0680 (1) |
O1—D4 | 1.0564 (1) | C2—O2 | 1.4212 (1) |
O1—D11i | 1.7262 (1) | C2—D8 | 1.0607 (1) |
D1—C1 | 1.1093 (1) | C2—D9 | 1.0931 (1) |
D1—D2 | 1.7737 (1) | C2—D10 | 1.1084 (1) |
D1—D3 | 1.8170 (1) | C2—D11 | 1.9462 (1) |
D2—C1 | 1.0891 (1) | O2—D5iv | 2.0584 (1) |
D2—O1 | 2.0641 (1) | O2—D7v | 2.0680 (1) |
D2—D1 | 1.7737 (1) | O2—C2 | 1.4212 (1) |
D2—D3 | 1.7588 (1) | O2—D10 | 2.0575 (1) |
D3—C1 | 1.1040 (1) | O2—D11 | 0.9987 (1) |
D3—O1 | 2.0557 (1) | D8—C2 | 1.0607 (1) |
D3—D1 | 1.8170 (1) | D8—D9 | 1.7587 (1) |
D3—D2 | 1.7588 (1) | D8—D10 | 1.7592 (1) |
D4—C1 | 2.0040 (1) | D9—C2 | 1.0931 (1) |
D4—O1 | 1.0564 (1) | D9—D8 | 1.7587 (1) |
D4—N1 | 1.6704 (1) | D9—D10 | 1.7517 (1) |
N1—D4 | 1.6704 (1) | D10—C2 | 1.1084 (1) |
N1—D5 | 1.0319 (1) | D10—O2 | 2.0575 (1) |
N1—D6 | 1.0327 (1) | D10—D8 | 1.7592 (1) |
N1—D7 | 0.9846 (1) | D10—D9 | 1.7517 (1) |
D5—N1 | 1.0319 (1) | D11—O1vi | 1.7262 (1) |
D5—D6 | 1.6213 (1) | D11—C2 | 1.9462 (1) |
D5—D7 | 1.6311 (1) | D11—O2 | 0.9987 (1) |
| | | |
O1—C1—D1 | 112.0788 (3) | D6—N1—D7 | 109.6988 (5) |
O1—C1—D2 | 110.8322 (1) | O2—C2—D8 | 114.7102 (3) |
O1—C1—D3 | 109.2208 (4) | O2—C2—D9 | 110.1865 (3) |
D1—C1—D2 | 107.5670 (1) | O2—C2—D10 | 108.2157 (6) |
D1—C1—D3 | 110.3599 (6) | D8—C2—D9 | 109.4762 (1) |
D2—C1—D3 | 106.6337 (5) | D8—C2—D10 | 108.3779 (5) |
C1—O1—D4 | 107.9420 (2) | D9—C2—D10 | 105.4401 (6) |
D5—N1—D6 | 103.4933 (5) | C2—O2—D11 | 105.7498 (8) |
D5—N1—D7 | 107.9495 (8) | | |
Symmetry codes: (i) x+1/2, y−1, −z+1/2; (ii) −x+1, y−1/2, −z+1; (iii) −x+1, y−1/2, −z; (iv) −x+1, y+1/2, −z+1; (v) −x+1, y+1/2, −z; (vi) x−1/2, y+1, −z+1/2. |
(METHANOL_HEMIAMMONIA_phase_1_180)
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Crystal data top
CD7NO | c = 7.6781 (2) Å |
Mr = 56.11 | V = 666.66 (2) Å3 |
Orthorhombic, Pbca | Z = 8 |
a = 11.2096 (3) Å | ? radiation, λ = ? Å |
b = 7.7456 (2) Å | ?; ?; ?; ?; ?, ?; ?; ?; ?; ? × ?; ?; ?; ?; ? mm |
Refinement top
Least-squares matrix: full | 844 data points |
Rp = 0.021 | Profile function: TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024090 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 6576.5 #6 (sig-2) = 23.1
#7 (gam-0) = 0.00 #8 (gam-1) = 18.72 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0, TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024090 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 2849.9 #6 (sig-2) = 451.6
#7 (gam-0) = 0.00 #8 (gam-1) = 0.00 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0 |
Rwp = 0.018 | 95 parameters |
Rexp = 0.005 | 46 restraints |
R(F2) = 0.30927 | (Δ/σ)max = 0.08 |
χ2 = 57.456 | Background function: GSAS Background function number 1 with 5 terms.
Shifted Chebyshev function of 1st kind
1: 1.21689 2: -0.177543 3: -4.811630E-02 4: 4.716540E-02
5: -2.750360E-02 |
Crystal data top
CD7NO | c = 7.6781 (2) Å |
Mr = 56.11 | V = 666.66 (2) Å3 |
Orthorhombic, Pbca | Z = 8 |
a = 11.2096 (3) Å | ? radiation, λ = ? Å |
b = 7.7456 (2) Å | ?; ?; ?; ?; ?, ?; ?; ?; ?; ? × ?; ?; ?; ?; ? mm |
Refinement top
Rp = 0.021 | χ2 = 57.456 |
Rwp = 0.018 | 844 data points |
Rexp = 0.005 | 95 parameters |
R(F2) = 0.30927 | 46 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C | 0.25504 | 0.0505 | 0.2268 | 0.05033 | |
O | 0.1338 | 0.01326 | 0.2297 | 0.034 | |
D1 | 0.27587 | 0.1712 | 0.271 | 0.16867 | |
D2 | 0.2875 | 0.0443 | 0.1019 | 0.17467 | |
D3 | 0.30029 | −0.0336 | 0.2982 | 0.138 | |
D4 | 0.09216 | 0.098 | 0.1593 | 0.04 | |
N | 0.49062 | 0.74732 | 1.03034 | 0.03467 | |
D5 | 0.54152 | 0.8274 | 1.1076 | 0.051 | |
D6 | 0.44586 | 0.823 | 0.9528 | 0.057 | |
D7 | 0.54881 | 0.67774 | 0.9542 | 0.05533 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C | 0.043 | 0.054 | 0.054 | −0.002 | −0.001 | 0.005 |
O | 0.037 | 0.021 | 0.044 | −0.008 | 0.001 | 0.01 |
D1 | 0.057 | 0.071 | 0.378 | −0.019 | −0.022 | −0.089 |
D2 | 0.1 | 0.338 | 0.086 | −0.055 | 0.03 | 0.017 |
D3 | 0.032 | 0.13 | 0.252 | 0.019 | −0.035 | 0.064 |
D4 | 0.036 | 0.036 | 0.048 | −0.004 | 0.01 | 0.003 |
N | 0.033 | 0.037 | 0.034 | 0.021 | −0.004 | 0.005 |
D5 | 0.063 | 0.059 | 0.031 | −0.011 | −0.07 | −0.02 |
D6 | 0.068 | 0.055 | 0.048 | −0.024 | −0.002 | −0.006 |
D7 | 0.047 | 0.047 | 0.072 | 0.011 | 0.012 | 0.003 |
Geometric parameters (Å, º) top
C—O | 1.3895 (1) | D3—O | 1.9727 (1) |
C—D1 | 1.0216 (1) | D3—D1 | 1.6232 (1) |
C—D2 | 1.0268 (1) | D3—D2 | 1.6298 (1) |
C—D3 | 0.9910 (1) | D4—C | 1.9333 (1) |
C—D4 | 1.9333 (1) | D4—O | 0.9700 (1) |
O—C | 1.3895 (1) | D4—Ni | 1.7830 (1) |
O—D1 | 2.0331 (1) | N—D4ii | 1.7830 (1) |
O—D2 | 1.9973 (1) | N—D5 | 1.0306 (1) |
O—D3 | 1.9727 (1) | N—D6 | 0.9746 (1) |
O—D4 | 0.9700 (1) | N—D7 | 1.0285 (1) |
D1—C | 1.0216 (1) | D5—N | 1.0306 (1) |
D1—O | 2.0331 (1) | D5—D6 | 1.6012 (1) |
D1—D2 | 1.6337 (1) | D5—D7 | 1.6546 (1) |
D1—D3 | 1.6232 (1) | D6—N | 0.9746 (1) |
D2—C | 1.0268 (1) | D6—D5 | 1.6012 (1) |
D2—O | 1.9973 (1) | D6—D7 | 1.6118 (1) |
D2—D1 | 1.6337 (1) | D7—N | 1.0285 (1) |
D2—D3 | 1.6298 (1) | D7—D5 | 1.6546 (1) |
D3—C | 0.9910 (1) | D7—D6 | 1.6118 (1) |
| | | |
O—C—D1 | 114.0910 (1) | D2—C—D3 | 107.7294 (14) |
O—C—D2 | 110.6005 (6) | C—O—D4 | 108.7395 (11) |
O—C—D3 | 110.8113 (12) | D5—N—D6 | 105.941 (2) |
D1—C—D2 | 105.7863 (7) | D5—N—D7 | 106.9442 (17) |
D1—C—D3 | 107.5033 (18) | D6—N—D7 | 107.1257 (19) |
Symmetry codes: (i) −x+1/2, y−1/2, z−1; (ii) −x+1/2, y+1/2, z+1. |
(METHANOL_HEMIAMMONIA_phase_2_180)
top
Crystal data top
C2D11.00NO2 | c = 4.79198 (4) Å |
Mr = 92.18 | V = 554.66 (1) Å3 |
Orthorhombic, Pn21a | Z = 4 |
a = 12.90413 (16) Å | ? radiation, λ = ? Å |
b = 8.96975 (8) Å | ?; ?; ?; ?; ?, ?; ?; ?; ?; ? × ?; ?; ?; ?; ? mm |
Refinement top
Least-squares matrix: full | 844 data points |
Rp = 0.021 | Profile function: TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024090 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 6576.5 #6 (sig-2) = 23.1
#7 (gam-0) = 0.00 #8 (gam-1) = 18.72 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0, TOF Profile function number 3 with 21 terms
Profile coefficients for exponential pseudovoigt
convolution Von Dreele, 1990 (unpublished)
#1 (alp ) = 0.1759 #2 (bet-0) = 0.024090 #3 (bet-1) = 0.007850
#4 (sig-0) = 0.0 #5 (sig-1) = 2849.9 #6 (sig-2) = 451.6
#7 (gam-0) = 0.00 #8 (gam-1) = 0.00 #9 (gam-2) = 0.00
#10(gsf ) = 0.00 #11(g1ec ) = 0.00 #12(g2ec ) = 0.00
#13(rstr ) = 0.000 #14(rsta ) = 0.000 #15(rsca ) = 0.000
#16(L11) = 0.000 #17(L22) = 0.000 #18(L33) = 0.000
#19(L12) = 0.000 #20(L13) = 0.000 #21(L23) = 0.000
Peak tails are ignored where the intensity is below 0.0010 times the peak
Aniso. broadening axis 0.0 0.0 1.0 |
Rwp = 0.018 | 95 parameters |
Rexp = 0.005 | 46 restraints |
R(F2) = 0.30927 | (Δ/σ)max = 0.08 |
χ2 = 57.456 | Background function: GSAS Background function number 1 with 5 terms.
Shifted Chebyshev function of 1st kind
1: 1.21689 2: -0.177543 3: -4.811630E-02 4: 4.716540E-02
5: -2.750360E-02 |
Crystal data top
C2D11.00NO2 | c = 4.79198 (4) Å |
Mr = 92.18 | V = 554.66 (1) Å3 |
Orthorhombic, Pn21a | Z = 4 |
a = 12.90413 (16) Å | ? radiation, λ = ? Å |
b = 8.96975 (8) Å | ?; ?; ?; ?; ?, ?; ?; ?; ?; ? × ?; ?; ?; ?; ? mm |
Refinement top
Rp = 0.021 | χ2 = 57.456 |
Rwp = 0.018 | 844 data points |
Rexp = 0.005 | 95 parameters |
R(F2) = 0.30927 | 46 restraints |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.5449 (2) | 0.2238 (3) | 0.0534 (5) | 0.0488 (10)* | |
O1 | 0.5684 (3) | 0.2320 (4) | 0.3440 (4) | 0.0391 (11)* | |
D1 | 0.5729 (6) | 0.3236 (6) | −0.0472 (9) | 0.068 (2)* | 0.607 (6) |
D2 | 0.4621 (2) | 0.2152 (11) | 0.0374 (9) | 0.050 (2)* | 0.607 (6) |
D3 | 0.5823 (6) | 0.1263 (7) | −0.0325 (10) | 0.080 (3)* | 0.607 (6) |
D4 | 0.5856 (2) | 0.3345 (4) | 0.3991 (6) | 0.0256 (9)* | |
N1 | 0.61410 (17) | 0.5248 (3) | 0.4604 (4) | 0.0346 (8)* | |
D5 | 0.6593 (2) | 0.5300 (5) | 0.6305 (5) | 0.0524 (12)* | |
D6 | 0.55341 (17) | 0.5941 (4) | 0.4829 (7) | 0.0613 (14)* | |
D7 | 0.6558 (3) | 0.5556 (5) | 0.2934 (5) | 0.0531 (13)* | |
C2 | 0.1840 (2) | 0.9041 (3) | 0.0101 (6) | 0.0712 (16)* | |
O2 | 0.2295 (3) | 1.0480 (3) | 0.0361 (6) | 0.0355 (12)* | |
D8 | 0.1110 (4) | 0.9120 (6) | −0.0899 (18) | 0.082 (4)* | 0.515 (8) |
D9 | 0.1744 (6) | 0.8626 (5) | 0.2255 (8) | 0.051 (3)* | 0.515 (8) |
D10 | 0.2370 (4) | 0.8328 (4) | −0.0995 (15) | 0.027 (2)* | 0.515 (8) |
D11 | 0.1761 (3) | 1.1255 (4) | 0.0667 (7) | 0.0471 (11)* | |
D1b | 0.4955 (8) | 0.3167 (8) | 0.0012 (9) | 0.053 (4)* | 0.393 (6) |
D2b | 0.5058 (9) | 0.1194 (7) | 0.0148 (10) | 0.041 (3)* | 0.393 (6) |
D3b | 0.6167 (3) | 0.2290 (15) | −0.0617 (7) | 0.046 (3)* | 0.393 (6) |
D8b | 0.1824 (8) | 0.8753 (7) | −0.2093 (8) | 0.056 (3)* | 0.485 (8) |
D9b | 0.1063 (4) | 0.9081 (5) | 0.092 (2) | 0.070 (4)* | 0.485 (8) |
D10b | 0.2308 (5) | 0.8254 (4) | 0.125 (2) | 0.141 (5)* | 0.485 (8) |
Geometric parameters (Å, º) top
C1—O1 | 1.427 (2) | O2—D10 | 2.039 (3) |
C1—D1 | 1.078 (3) | O2—D11 | 0.990 (3) |
C1—D2 | 1.075 (3) | O2—D8b | 2.0372 (18) |
C1—D3 | 1.080 (3) | O2—D9b | 2.0424 (18) |
C1—D4 | 2.001 (4) | O2—D10b | 2.0408 (18) |
C1—D1b | 1.0787 (17) | D8—C2 | 1.060 (3) |
C1—D2b | 1.0799 (17) | D8—O2 | 2.047 (4) |
C1—D3b | 1.0784 (16) | D8—D9 | 1.7749 (8) |
O1—C1 | 1.427 (2) | D8—D10 | 1.7752 (8) |
O1—D1 | 2.047 (3) | D8—D8b | 1.134 (6) |
O1—D2 | 2.016 (3) | D8—D9b | 0.876 (7) |
O1—D3 | 2.046 (3) | D9—C2 | 1.104 (3) |
O1—D4 | 0.982 (3) | D9—O2 | 2.023 (3) |
O1—D11i | 1.740 (5) | D9—D8 | 1.7749 (8) |
O1—D1b | 2.0397 (18) | D9—D10 | 1.7749 (8) |
O1—D2b | 2.0398 (18) | D9—D9b | 1.160 (7) |
O1—D3b | 2.0415 (18) | D9—D10b | 0.935 (8) |
D1—C1 | 1.078 (3) | D10—C2 | 1.074 (3) |
D1—O1 | 2.047 (3) | D10—O2 | 2.039 (3) |
D1—D2 | 1.7752 (8) | D10—D8 | 1.7752 (8) |
D1—D3 | 1.7746 (8) | D10—D9 | 1.7749 (8) |
D1—D1b | 1.026 (7) | D10—D8b | 0.958 (7) |
D1—D3b | 1.022 (7) | D10—D10b | 1.079 (7) |
D2—C1 | 1.075 (3) | D11—O1ii | 1.740 (5) |
D2—O1 | 2.016 (3) | D11—C2 | 2.007 (4) |
D2—D1 | 1.7752 (8) | D11—O2 | 0.990 (3) |
D2—D3 | 1.7754 (8) | D1b—C1 | 1.0787 (17) |
D2—D1b | 1.022 (7) | D1b—O1 | 2.0397 (18) |
D2—D2b | 1.034 (7) | D1b—D1 | 1.026 (7) |
D3—C1 | 1.080 (3) | D1b—D2 | 1.022 (7) |
D3—O1 | 2.046 (3) | D1b—D2b | 1.7760 (18) |
D3—D1 | 1.7746 (8) | D1b—D3b | 1.7757 (18) |
D3—D2 | 1.7754 (8) | D2b—C1 | 1.0799 (17) |
D3—D2b | 1.014 (7) | D2b—O1 | 2.0398 (18) |
D3—D3b | 1.032 (7) | D2b—D2 | 1.034 (7) |
D4—C1 | 2.001 (4) | D2b—D3 | 1.014 (7) |
D4—O1 | 0.982 (3) | D2b—D1b | 1.7760 (18) |
D4—N1 | 1.770 (4) | D2b—D3b | 1.7737 (18) |
N1—D4 | 1.770 (4) | D3b—C1 | 1.0784 (16) |
N1—D5 | 1.0034 (16) | D3b—O1 | 2.0415 (18) |
N1—D6 | 1.0061 (16) | D3b—D1 | 1.022 (7) |
N1—D7 | 1.0035 (16) | D3b—D3 | 1.032 (7) |
D5—N1 | 1.0034 (16) | D3b—D1b | 1.7757 (18) |
D5—D6 | 1.6423 (18) | D3b—D2b | 1.7737 (18) |
D5—D7 | 1.6325 (18) | D8b—C2 | 1.0831 (17) |
D6—N1 | 1.0061 (16) | D8b—O2 | 2.0372 (18) |
D6—D5 | 1.6423 (18) | D8b—D8 | 1.134 (6) |
D6—D7 | 1.6404 (18) | D8b—D10 | 0.958 (7) |
D7—N1 | 1.0035 (16) | D8b—D9b | 1.7718 (18) |
D7—D5 | 1.6325 (18) | D8b—D10b | 1.7755 (18) |
D7—D6 | 1.6404 (18) | D9b—C2 | 1.0777 (17) |
C2—O2 | 1.423 (2) | D9b—O2 | 2.0424 (18) |
C2—D8 | 1.060 (3) | D9b—D8 | 0.876 (7) |
C2—D9 | 1.104 (3) | D9b—D9 | 1.160 (7) |
C2—D10 | 1.074 (3) | D9b—D8b | 1.7718 (18) |
C2—D11 | 2.007 (4) | D9b—D10b | 1.7763 (18) |
C2—D8b | 1.0831 (17) | D10b—C2 | 1.0792 (17) |
C2—D9b | 1.0777 (17) | D10b—O2 | 2.0408 (18) |
C2—D10b | 1.0792 (17) | D10b—D9 | 0.935 (8) |
O2—C2 | 1.423 (2) | D10b—D10 | 1.079 (7) |
O2—D8 | 2.047 (4) | D10b—D8b | 1.7755 (18) |
O2—D9 | 2.023 (3) | D10b—D9b | 1.7763 (18) |
| | | |
O1—C1—D1 | 108.8 (3) | D8—C2—D8b | 63.9 (4) |
O1—C1—D2 | 106.5 (3) | D8—C2—D9b | 48.4 (4) |
O1—C1—D3 | 108.6 (3) | D8—C2—D10b | 140.5 (4) |
O1—C1—D1b | 108.19 (19) | D9—C2—D10 | 109.2 (3) |
O1—C1—D2b | 108.13 (19) | D9—C2—D8b | 145.6 (4) |
O1—C1—D3b | 108.35 (19) | D9—C2—D9b | 64.2 (4) |
D1—C1—D2 | 111.1 (3) | D9—C2—D10b | 50.7 (4) |
D1—C1—D3 | 110.6 (2) | D10—C2—D8b | 52.8 (4) |
D1—C1—D1b | 56.8 (4) | D10—C2—D9b | 142.2 (4) |
D1—C1—D2b | 143.0 (4) | D10—C2—D10b | 60.2 (4) |
D1—C1—D3b | 56.6 (4) | D8b—C2—D9b | 110.2 (2) |
D2—C1—D3 | 111.0 (3) | D8b—C2—D10b | 110.4 (2) |
D2—C1—D1b | 56.7 (4) | D9b—C2—D10b | 110.9 (2) |
D2—C1—D2b | 57.4 (4) | C2—O2—D11 | 111.3 (3) |
D2—C1—D3b | 145.1 (3) | C2—D8—D8b | 59.1 (2) |
D3—C1—D1b | 143.2 (4) | C2—D8—D9b | 66.9 (3) |
D3—C1—D2b | 56.0 (4) | D8b—D8—D9b | 123.2 (4) |
D3—C1—D3b | 57.1 (4) | C2—D9—D9b | 56.8 (2) |
D1b—C1—D2b | 110.7 (2) | C2—D9—D10b | 63.3 (3) |
D1b—C1—D3b | 110.8 (2) | D9b—D9—D10b | 115.5 (4) |
D2b—C1—D3b | 110.5 (2) | C2—D10—D8b | 64.1 (3) |
C1—O1—D4 | 111.0 (3) | C2—D10—D10b | 60.2 (3) |
C1—D1—D1b | 61.6 (2) | D8b—D10—D10b | 121.1 (4) |
C1—D1—D3b | 61.7 (3) | C1—D1b—D1 | 61.6 (3) |
D1b—D1—D3b | 120.2 (4) | C1—D1b—D2 | 61.5 (3) |
C1—D2—D1b | 61.9 (2) | D1—D1b—D2 | 120.1 (4) |
C1—D2—D2b | 61.6 (2) | C1—D2b—D2 | 61.1 (2) |
D1b—D2—D2b | 119.5 (3) | C1—D2b—D3 | 62.0 (3) |
C1—D3—D2b | 62.0 (2) | D2—D2b—D3 | 120.2 (4) |
C1—D3—D3b | 61.4 (3) | C1—D3b—D1 | 61.7 (2) |
D2b—D3—D3b | 120.3 (4) | C1—D3b—D3 | 61.5 (2) |
D5—N1—D6 | 109.6 (2) | D1—D3b—D3 | 119.6 (3) |
D5—N1—D7 | 108.9 (2) | C2—D8b—D8 | 57.1 (2) |
D6—N1—D7 | 109.4 (2) | C2—D8b—D10 | 63.1 (3) |
O2—C2—D8 | 110.2 (3) | D8—D8b—D10 | 115.8 (4) |
O2—C2—D9 | 105.7 (3) | C2—D9b—D8 | 64.8 (3) |
O2—C2—D10 | 108.7 (3) | C2—D9b—D9 | 59.0 (3) |
O2—C2—D8b | 108.0 (2) | D8—D9b—D9 | 120.7 (4) |
O2—C2—D9b | 108.8 (2) | C2—D10b—D9 | 66.0 (3) |
O2—C2—D10b | 108.5 (2) | C2—D10b—D10 | 59.7 (2) |
D8—C2—D9 | 110.2 (3) | D9—D10b—D10 | 123.3 (4) |
D8—C2—D10 | 112.6 (3) | | |
Symmetry codes: (i) x+1/2, y−1, −z+1/2; (ii) x−1/2, y+1, −z+1/2. |
Experimental details
| (METHANOL_HEMIAMMONIA_phase_1) | (METHANOL_HEMIAMMONIA_phase_2) | (METHANOL_HEMIAMMONIA_phase_1_180) | (METHANOL_HEMIAMMONIA_phase_2_180) |
Crystal data |
Chemical formula | CD7NO | C2D11NO2 | CD7NO | C2D11.00NO2 |
Mr | 56.11 | 92.18 | 56.11 | 92.18 |
Crystal system, space group | Orthorhombic, Pbca | Orthorhombic, Pn21a | Orthorhombic, Pbca | Orthorhombic, Pn21a |
Temperature (K) | ? | ? | ? | ? |
a, b, c (Å) | 11.0386 (4), 7.6547 (3), 7.5847 (3) | 12.70615 (16), 8.84589 (9), 4.73876 (4) | 11.2096 (3), 7.7456 (2), 7.6781 (2) | 12.90413 (16), 8.96975 (8), 4.79198 (4) |
V (Å3) | 640.88 (3) | 532.62 (1) | 666.66 (2) | 554.66 (1) |
Z | 8 | 4 | 8 | 4 |
Radiation type | ?, λ = ? Å | ?, λ = ? Å | ?, λ = ? Å | ?, λ = ? Å |
Specimen shape, size (mm) | ?; ?; ?, ?; ?; ? × ?; ?; ? | ?; ?; ?, ?; ?; ? × ?; ?; ? | ?; ?; ?; ?; ?, ?; ?; ?; ?; ? × ?; ?; ?; ?; ? | ?; ?; ?; ?; ?, ?; ?; ?; ?; ? × ?; ?; ?; ?; ? |
|
Data collection |
Diffractometer | ?; ?; ? | ?; ?; ? | ?; ?; ?; ?; ? | ?; ?; ?; ?; ? |
Specimen mounting | ?; ?; ? | ?; ?; ? | ?; ?; ?; ?; ? | ?; ?; ?; ?; ? |
Data collection mode | ?; ?; ? | ?; ?; ? | ?; ?; ?; ?; ? | ?; ?; ?; ?; ? |
Scan method | ?; ?; ? | ?; ?; ? | ?; ?; ?; ?; ? | ?; ?; ?; ?; ? |
2θ values (°) | 2θmin = ? 2θmax = ? 2θstep = ? | 2θmin = ? 2θmax = ? 2θstep = ? | 2θmin = ? 2θmax = ? 2θstep = ? | 2θmin = ? 2θmax = ? 2θstep = ? |
|
Refinement |
R factors and goodness of fit | Rp = 0.023, Rwp = 0.027, Rexp = 0.009, R(F2) = 0.05592, χ2 = 54.317 | Rp = 0.023, Rwp = 0.027, Rexp = 0.009, R(F2) = 0.05592, χ2 = 54.317 | Rp = 0.021, Rwp = 0.018, Rexp = 0.005, R(F2) = 0.30927, χ2 = 57.456 | Rp = 0.021, Rwp = 0.018, Rexp = 0.005, R(F2) = 0.30927, χ2 = 57.456 |
No. of data points | 4404 | 4404 | 844 | 844 |
No. of parameters | 5 | 5 | 95 | 95 |
No. of restraints | 22 | 22 | 46 | 46 |
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