Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107051396/sf3055sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107051396/sf3055S2.HClsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107051396/sf3055R3sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107051396/sf3055S3sup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107051396/sf3055R4sup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107051396/sf3055S4sup6.hkl |
CCDC references: 677212; 677213; 677214; 677215; 677216
For related literature, see: Ahrendt et al. (2000); Almaşi et al. (2007); Amos (1995); Beeson & MacMillan (2005); Bernstein (2002); Bolm et al. (2005); Brochu et al. (2004); Gaunt et al. (2007); Hassinen & Peräkylä (2001); Jen et al. (2000); Kunz & MacMillan (2005); List (2006); Marigo et al. (2005); Mourik et al. (2006); Paras & MacMillan (2001); Tsogoeva (2007); Wilson et al. (2005).
For the synthesis of the catalyst, 5(S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one was synthesized from commercially available (S)-phenylalanine methylester hydrochloride according to the literature method described by Ahrendt et al. (2000). Treatment of (S)-phenylalanine methylester hydrochloride with ethanolic methylamine furnished the intermediate (S)-phenylalanine N-methyl amide hydrochloride, which was not isolated, but heated to reflux in MeOH and acetone with catalytic para-toluenesulfonic acid (p-TSA). The cyclized (S)-imidazolidinone product was precipitated as the HCl salt and recrystallized from 2-propanol to yield a microcrystalline white needle-like material, which was identical to that previously characterized. The (R)-enantiomer was prepared in an identical manner starting from commercially available (R)-phenylalanine methylamide hydrochloride. This material displayed identical 1H and 13C NMR spectra to the (S)-enantiomer, and had an equal but opposite optical rotation value, as expected. A simplified reaction scheme is shown in the Comment section.
Initial attempts to grow large crystals by slow evaporation (several months, 277 K) from CHCl3 were successful in this aim, but crystallographic characterization indicated that ring opening of the imidazolidinone had occurred to yield (R/S)-phenylalanine methylamide hydrochloride. As the crystal structure of this material had not been reported, a full data set was collected on the (S) isomer and is reported here. Crystals of 5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride were grown by rapid evaporation (ca 2 days, ambient temperature) from CHCl3. Samples of 5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride hydrate were crystallized from 2-propanol as a microcrystalline powder and correspond to the `raw' reagent described in the synthesis; these were subject to standard benchtop storage conditions for several months after crystallization.
Single crystals were selected, mounted at the end of two-stage glass fibres and studied at 150 K on station 9.8 or station 16.2 SMX of the UK Synchrotron Radiation Source, Daresbury. Routine data collection involved three series of ω scans. Data were corrected for beam decay and absorption using a method based on equivalents. Further details can be found in the relevant section of the CIF that accompanies this paper.
Computational studies were performed to investigate the conformational energy landscape of the molecular cations. For both protonated (R/S)-phenylalanine methylamide and for the imidazolidinone cation, initial calculations were performed using a simple molecular mechanics model (Tripos 5.2) as implemented in Ghemical (Hassinen & Peräkylä, 2001). For the imidazolidinone cation, for which the potential energy landscape was relatively complex, the three local minima located in the initial molecular mechanics search were investigated at a higher level of theory. The three molecular mechanics energy minima were energy minimized using both B3LYP/6–31 G(d,p) and B3LYP/6–311 G(d,p) levels of theory, giving refined gas phase molecular structures and their relative energies. All density functional theory calculations were performed using the program CADPAC (Amos, 1995).
Data collection: APEX2 (Bruker, 2004) for S2.HCl, R3, S3, R4; APEXII (Bruker, 2004) for S4. Cell refinement: APEX2 (Bruker, 2004) for S2.HCl, R3, S3, R4; APEXII (Bruker, 2004) for S4. Data reduction: APEX2 (Bruker, 2004) for S2.HCl, R3, S3, R4; APEXII (Bruker, 2004) for S4. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Version 1.64; Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C10H15N2O+·Cl− | F(000) = 456 |
Mr = 214.69 | Dx = 1.303 Mg m−3 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.69040 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2000 reflections |
a = 4.9758 (7) Å | θ = 2.4–24.5° |
b = 8.6213 (13) Å | µ = 0.32 mm−1 |
c = 25.521 (4) Å | T = 150 K |
V = 1094.8 (3) Å3 | Block, colourless |
Z = 4 | 0.15 × 0.07 × 0.07 mm |
Bruker D8 diffractometer | 3619 independent reflections |
Radiation source: Daresbury SRS, Station 16.2SMX | 2971 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.091 |
ω rotation with narrow frame scans | θmax = 31.2°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −7→7 |
Tmin = 0.953, Tmax = 0.978 | k = −12→12 |
12758 measured reflections | l = −36→36 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.157 | w = 1/[σ2(Fo2) + (0.0882P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
3619 reflections | Δρmax = 0.58 e Å−3 |
141 parameters | Δρmin = −0.57 e Å−3 |
4 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (9) |
C10H15N2O+·Cl− | V = 1094.8 (3) Å3 |
Mr = 214.69 | Z = 4 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.69040 Å |
a = 4.9758 (7) Å | µ = 0.32 mm−1 |
b = 8.6213 (13) Å | T = 150 K |
c = 25.521 (4) Å | 0.15 × 0.07 × 0.07 mm |
Bruker D8 diffractometer | 3619 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2971 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 0.978 | Rint = 0.091 |
12758 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.157 | Δρmax = 0.58 e Å−3 |
S = 1.00 | Δρmin = −0.57 e Å−3 |
3619 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
141 parameters | Absolute structure parameter: −0.01 (9) |
4 restraints |
Experimental. A correction to account for beam decay and absorption was applied using SADABS. The ratio of max to min apparent transmission was 0.748 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.80225 (12) | 0.77857 (7) | 0.21217 (2) | 0.02442 (15) | |
C1 | 0.5003 (6) | 0.4375 (3) | 0.03794 (10) | 0.0265 (5) | |
H1 | 0.6370 | 0.3934 | 0.0578 | 0.032* | |
C2 | 0.4683 (6) | 0.3934 (3) | −0.01397 (11) | 0.0309 (6) | |
H2 | 0.5831 | 0.3205 | −0.0288 | 0.037* | |
C3 | 0.2642 (6) | 0.4586 (3) | −0.04355 (10) | 0.0290 (6) | |
H3 | 0.2419 | 0.4292 | −0.0783 | 0.035* | |
C4 | 0.0933 (6) | 0.5672 (3) | −0.02155 (10) | 0.0306 (6) | |
H4 | −0.0431 | 0.6112 | −0.0416 | 0.037* | |
C5 | 0.1262 (6) | 0.6104 (3) | 0.03054 (10) | 0.0266 (5) | |
H5 | 0.0099 | 0.6826 | 0.0454 | 0.032* | |
C6 | 0.3310 (5) | 0.5468 (3) | 0.06072 (9) | 0.0220 (4) | |
C7 | 0.3747 (6) | 0.5994 (3) | 0.11668 (9) | 0.0246 (5) | |
H7A | 0.2988 | 0.7023 | 0.1209 | 0.029* | |
H7B | 0.5663 | 0.6067 | 0.1232 | 0.029* | |
C8 | 0.2494 (5) | 0.4913 (3) | 0.15748 (9) | 0.0210 (5) | |
H8 | 0.0559 | 0.4830 | 0.1509 | 0.025* | |
C9 | 0.3736 (5) | 0.3295 (3) | 0.15676 (9) | 0.0205 (4) | |
O10 | 0.6195 (4) | 0.3128 (2) | 0.16136 (8) | 0.0290 (4) | |
N11 | 0.1991 (4) | 0.2140 (2) | 0.15128 (8) | 0.0211 (4) | |
H11 | 0.031 (4) | 0.236 (4) | 0.1547 (11) | 0.036 (4)* | |
C12 | 0.2767 (6) | 0.0524 (3) | 0.15529 (10) | 0.0293 (6) | |
H12A | 0.1576 | −0.0001 | 0.1790 | 0.044* | |
H12B | 0.4575 | 0.0455 | 0.1682 | 0.044* | |
H12C | 0.2664 | 0.0048 | 0.1213 | 0.044* | |
N16 | 0.2938 (4) | 0.5585 (2) | 0.21067 (8) | 0.0218 (4) | |
H16A | 0.176 (6) | 0.632 (3) | 0.2181 (12) | 0.036 (4)* | |
H16B | 0.282 (7) | 0.491 (3) | 0.2370 (9) | 0.036 (4)* | |
H16C | 0.451 (5) | 0.605 (4) | 0.2140 (13) | 0.036 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0236 (3) | 0.0211 (2) | 0.0285 (3) | 0.0000 (2) | 0.0011 (2) | −0.0047 (2) |
C1 | 0.0216 (12) | 0.0296 (13) | 0.0284 (12) | 0.0018 (11) | −0.0031 (10) | 0.0009 (10) |
C2 | 0.0295 (15) | 0.0334 (13) | 0.0297 (12) | 0.0031 (11) | −0.0001 (11) | −0.0020 (11) |
C3 | 0.0276 (14) | 0.0347 (13) | 0.0246 (11) | −0.0021 (11) | −0.0046 (9) | 0.0001 (9) |
C4 | 0.0298 (14) | 0.0312 (13) | 0.0309 (13) | 0.0002 (11) | −0.0053 (11) | 0.0048 (10) |
C5 | 0.0253 (13) | 0.0233 (11) | 0.0312 (12) | 0.0030 (10) | −0.0021 (10) | 0.0001 (10) |
C6 | 0.0220 (12) | 0.0200 (9) | 0.0238 (10) | −0.0030 (9) | −0.0015 (9) | 0.0024 (8) |
C7 | 0.0295 (13) | 0.0173 (10) | 0.0269 (11) | −0.0031 (9) | 0.0006 (10) | 0.0019 (9) |
C8 | 0.0189 (12) | 0.0185 (9) | 0.0256 (10) | 0.0000 (8) | 0.0001 (8) | −0.0001 (8) |
C9 | 0.0204 (11) | 0.0191 (10) | 0.0220 (10) | 0.0017 (9) | 0.0016 (8) | 0.0021 (8) |
O10 | 0.0176 (8) | 0.0256 (9) | 0.0440 (11) | 0.0024 (7) | −0.0012 (8) | −0.0014 (7) |
N11 | 0.0195 (9) | 0.0175 (8) | 0.0263 (9) | −0.0007 (9) | 0.0025 (8) | −0.0016 (7) |
C12 | 0.0324 (14) | 0.0170 (10) | 0.0385 (13) | 0.0000 (10) | 0.0042 (11) | 0.0021 (9) |
N16 | 0.0210 (9) | 0.0192 (8) | 0.0252 (9) | −0.0008 (8) | 0.0037 (9) | 0.0004 (7) |
C1—C2 | 1.388 (4) | C7—H7B | 0.9700 |
C1—C6 | 1.391 (4) | C8—N16 | 1.492 (3) |
C1—H1 | 0.9300 | C8—C9 | 1.526 (3) |
C2—C3 | 1.384 (4) | C8—H8 | 0.9800 |
C2—H2 | 0.9300 | C9—O10 | 1.238 (3) |
C3—C4 | 1.384 (4) | C9—N11 | 1.328 (3) |
C3—H3 | 0.9300 | N11—C12 | 1.449 (3) |
C4—C5 | 1.390 (4) | N11—H11 | 0.864 (18) |
C4—H4 | 0.9300 | C12—H12A | 0.9600 |
C5—C6 | 1.390 (3) | C12—H12B | 0.9600 |
C5—H5 | 0.9300 | C12—H12C | 0.9600 |
C6—C7 | 1.514 (3) | N16—H16A | 0.883 (18) |
C7—C8 | 1.530 (3) | N16—H16B | 0.892 (17) |
C7—H7A | 0.9700 | N16—H16C | 0.880 (18) |
C2—C1—C6 | 121.0 (2) | N16—C8—C9 | 107.81 (18) |
C2—C1—H1 | 119.5 | N16—C8—C7 | 108.84 (19) |
C6—C1—H1 | 119.5 | C9—C8—C7 | 112.6 (2) |
C3—C2—C1 | 119.6 (3) | N16—C8—H8 | 109.2 |
C3—C2—H2 | 120.2 | C9—C8—H8 | 109.2 |
C1—C2—H2 | 120.2 | C7—C8—H8 | 109.2 |
C4—C3—C2 | 120.3 (2) | O10—C9—N11 | 124.7 (2) |
C4—C3—H3 | 119.9 | O10—C9—C8 | 120.3 (2) |
C2—C3—H3 | 119.9 | N11—C9—C8 | 115.0 (2) |
C3—C4—C5 | 119.8 (3) | C9—N11—C12 | 122.6 (2) |
C3—C4—H4 | 120.1 | C9—N11—H11 | 117 (2) |
C5—C4—H4 | 120.1 | C12—N11—H11 | 118 (2) |
C6—C5—C4 | 120.7 (2) | N11—C12—H12A | 109.5 |
C6—C5—H5 | 119.7 | N11—C12—H12B | 109.5 |
C4—C5—H5 | 119.7 | H12A—C12—H12B | 109.5 |
C5—C6—C1 | 118.7 (2) | N11—C12—H12C | 109.5 |
C5—C6—C7 | 120.6 (2) | H12A—C12—H12C | 109.5 |
C1—C6—C7 | 120.7 (2) | H12B—C12—H12C | 109.5 |
C6—C7—C8 | 113.7 (2) | C8—N16—H16A | 112 (2) |
C6—C7—H7A | 108.8 | C8—N16—H16B | 115 (2) |
C8—C7—H7A | 108.8 | H16A—N16—H16B | 105 (3) |
C6—C7—H7B | 108.8 | C8—N16—H16C | 113 (2) |
C8—C7—H7B | 108.8 | H16A—N16—H16C | 104 (3) |
H7A—C7—H7B | 107.7 | H16B—N16—H16C | 106 (3) |
C13H19N2O+·Cl− | F(000) = 1632 |
Mr = 254.75 | Dx = 1.221 Mg m−3 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.69040 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2939 reflections |
a = 7.1167 (14) Å | θ = 2.6–23.5° |
b = 19.237 (4) Å | µ = 0.26 mm−1 |
c = 30.370 (6) Å | T = 150 K |
V = 4157.7 (14) Å3 | Block, colourless |
Z = 12 | 0.1 × 0.08 × 0.04 mm |
Bruker D8 diffractometer | 9772 independent reflections |
Radiation source: Daresbury SRS, Station 16.2SMX | 7354 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.071 |
ω rotation with narrow frame scans | θmax = 27.2°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→8 |
Tmin = 0.974, Tmax = 0.990 | k = −25→24 |
24370 measured reflections | l = −37→40 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0431P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
9772 reflections | Δρmax = 0.28 e Å−3 |
488 parameters | Δρmin = −0.23 e Å−3 |
6 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (6) |
C13H19N2O+·Cl− | V = 4157.7 (14) Å3 |
Mr = 254.75 | Z = 12 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.69040 Å |
a = 7.1167 (14) Å | µ = 0.26 mm−1 |
b = 19.237 (4) Å | T = 150 K |
c = 30.370 (6) Å | 0.1 × 0.08 × 0.04 mm |
Bruker D8 diffractometer | 9772 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 7354 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.990 | Rint = 0.071 |
24370 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.131 | Δρmax = 0.28 e Å−3 |
S = 0.99 | Δρmin = −0.23 e Å−3 |
9772 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
488 parameters | Absolute structure parameter: 0.00 (6) |
6 restraints |
Experimental. A correction to account for beam decay and absorption was applied using SADABS. The ratio of max to min apparent transmission was 0.692. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Ffrom the least squares refinement, Flack x parameter = 0.0036 e.s.d. 0.0555 |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.46650 (11) | 0.67659 (4) | 0.20932 (2) | 0.03596 (17) | |
Cl2 | 0.03772 (12) | 0.29717 (4) | 0.03881 (2) | 0.03702 (17) | |
Cl3 | 0.95538 (11) | 0.74670 (4) | 0.12677 (2) | 0.03563 (17) | |
C1 | 0.7744 (6) | 0.46455 (15) | 0.01218 (11) | 0.0456 (9) | |
H1 | 0.8945 | 0.4544 | 0.0242 | 0.055* | |
C2 | 0.7600 (7) | 0.50897 (18) | −0.02362 (13) | 0.0585 (11) | |
H2 | 0.8698 | 0.5290 | −0.0360 | 0.070* | |
C3 | 0.5861 (7) | 0.52401 (18) | −0.04115 (12) | 0.0638 (12) | |
H3 | 0.5757 | 0.5548 | −0.0655 | 0.077* | |
C4 | 0.4280 (7) | 0.49429 (17) | −0.02337 (11) | 0.0564 (11) | |
H4 | 0.3083 | 0.5044 | −0.0356 | 0.068* | |
C5 | 0.4418 (6) | 0.44972 (16) | 0.01234 (10) | 0.0473 (9) | |
H5 | 0.3316 | 0.4293 | 0.0244 | 0.057* | |
C6 | 0.6155 (5) | 0.43491 (14) | 0.03055 (10) | 0.0376 (8) | |
C7 | 0.6356 (5) | 0.39431 (14) | 0.07324 (10) | 0.0353 (7) | |
H7A | 0.5985 | 0.4254 | 0.0977 | 0.042* | |
H7B | 0.7705 | 0.3834 | 0.0772 | 0.042* | |
C8 | 0.5259 (5) | 0.32682 (13) | 0.07814 (8) | 0.0293 (6) | |
H8 | 0.3928 | 0.3337 | 0.0685 | 0.035* | |
C9 | 0.5317 (4) | 0.30392 (14) | 0.12622 (9) | 0.0311 (6) | |
O10 | 0.5073 (3) | 0.34214 (10) | 0.15770 (6) | 0.0437 (6) | |
N11 | 0.5659 (4) | 0.23550 (11) | 0.12752 (7) | 0.0308 (5) | |
C12 | 0.5528 (5) | 0.19533 (16) | 0.16773 (9) | 0.0390 (7) | |
H12A | 0.5590 | 0.2266 | 0.1931 | 0.058* | |
H12B | 0.6572 | 0.1622 | 0.1691 | 0.058* | |
H12C | 0.4333 | 0.1700 | 0.1682 | 0.058* | |
C13 | 0.5733 (4) | 0.20211 (14) | 0.08390 (9) | 0.0304 (7) | |
C14 | 0.3854 (5) | 0.16930 (16) | 0.07276 (10) | 0.0414 (8) | |
H14A | 0.3562 | 0.1330 | 0.0944 | 0.062* | |
H14B | 0.3915 | 0.1487 | 0.0433 | 0.062* | |
H14C | 0.2871 | 0.2050 | 0.0734 | 0.062* | |
C15 | 0.7356 (5) | 0.15277 (16) | 0.07957 (10) | 0.0405 (8) | |
H15A | 0.8506 | 0.1754 | 0.0901 | 0.061* | |
H15B | 0.7510 | 0.1396 | 0.0486 | 0.061* | |
H15C | 0.7112 | 0.1111 | 0.0972 | 0.061* | |
N16 | 0.6093 (4) | 0.26534 (12) | 0.05525 (8) | 0.0291 (5) | |
H16A | 0.730 (3) | 0.2719 (17) | 0.0534 (11) | 0.041 (4)* | |
H16B | 0.576 (5) | 0.2568 (15) | 0.0282 (7) | 0.041 (4)* | |
C21 | 1.1491 (5) | 0.52093 (16) | 0.20431 (11) | 0.0439 (8) | |
H21 | 1.2265 | 0.5252 | 0.2297 | 0.053* | |
C22 | 1.2151 (6) | 0.48585 (16) | 0.16804 (11) | 0.0482 (9) | |
H22 | 1.3371 | 0.4658 | 0.1684 | 0.058* | |
C23 | 1.1041 (6) | 0.47985 (15) | 0.13141 (11) | 0.0471 (9) | |
H23 | 1.1482 | 0.4545 | 0.1066 | 0.057* | |
C24 | 0.9307 (6) | 0.51003 (16) | 0.13026 (11) | 0.0500 (9) | |
H24 | 0.8562 | 0.5072 | 0.1044 | 0.060* | |
C25 | 0.8636 (5) | 0.54468 (15) | 0.16681 (10) | 0.0414 (8) | |
H25 | 0.7420 | 0.5650 | 0.1660 | 0.050* | |
C26 | 0.9706 (5) | 0.55017 (13) | 0.20433 (9) | 0.0328 (6) | |
C27 | 0.8962 (4) | 0.58805 (14) | 0.24435 (9) | 0.0329 (7) | |
H27A | 0.9219 | 0.5596 | 0.2709 | 0.039* | |
H27B | 0.7583 | 0.5929 | 0.2416 | 0.039* | |
C28 | 0.9821 (4) | 0.66006 (13) | 0.25076 (9) | 0.0298 (6) | |
H28 | 1.1179 | 0.6586 | 0.2423 | 0.036* | |
C29 | 0.9646 (4) | 0.68746 (14) | 0.29762 (9) | 0.0304 (6) | |
O30 | 0.9865 (3) | 0.65260 (10) | 0.33076 (6) | 0.0404 (5) | |
N31 | 0.9272 (4) | 0.75559 (12) | 0.29557 (7) | 0.0308 (5) | |
C32 | 0.9406 (5) | 0.80102 (16) | 0.33398 (9) | 0.0403 (8) | |
H32A | 0.9329 | 0.7730 | 0.3609 | 0.060* | |
H32B | 0.8371 | 0.8346 | 0.3335 | 0.060* | |
H32C | 1.0607 | 0.8259 | 0.3333 | 0.060* | |
C33 | 0.9131 (4) | 0.78357 (14) | 0.25062 (9) | 0.0305 (7) | |
C34 | 1.0940 (5) | 0.81854 (16) | 0.23651 (11) | 0.0412 (8) | |
H34A | 1.1203 | 0.8578 | 0.2561 | 0.062* | |
H34B | 1.0811 | 0.8354 | 0.2062 | 0.062* | |
H34C | 1.1975 | 0.7850 | 0.2381 | 0.062* | |
C35 | 0.7443 (5) | 0.82979 (16) | 0.24437 (10) | 0.0385 (7) | |
H35A | 0.6327 | 0.8069 | 0.2565 | 0.058* | |
H35B | 0.7256 | 0.8386 | 0.2129 | 0.058* | |
H35C | 0.7649 | 0.8740 | 0.2597 | 0.058* | |
N36 | 0.8859 (4) | 0.71663 (13) | 0.22517 (8) | 0.0293 (5) | |
H36A | 0.935 (5) | 0.7194 (16) | 0.1989 (7) | 0.041 (4)* | |
H36B | 0.765 (3) | 0.7066 (17) | 0.2250 (11) | 0.041 (4)* | |
C41 | 0.6783 (5) | 0.91208 (17) | 0.12749 (11) | 0.0409 (7) | |
H41 | 0.7310 | 0.8807 | 0.1067 | 0.049* | |
C42 | 0.7844 (5) | 0.96729 (16) | 0.14272 (10) | 0.0419 (8) | |
H42 | 0.9094 | 0.9731 | 0.1324 | 0.050* | |
C43 | 0.7130 (5) | 1.01334 (16) | 0.17222 (11) | 0.0450 (8) | |
H43 | 0.7867 | 1.0511 | 0.1826 | 0.054* | |
C44 | 0.5314 (6) | 1.00407 (17) | 0.18681 (13) | 0.0597 (10) | |
H44 | 0.4794 | 1.0361 | 0.2073 | 0.072* | |
C45 | 0.4241 (5) | 0.94923 (16) | 0.17223 (12) | 0.0487 (9) | |
H45 | 0.2995 | 0.9435 | 0.1828 | 0.058* | |
C46 | 0.4971 (4) | 0.90207 (14) | 0.14203 (9) | 0.0321 (7) | |
C47 | 0.3752 (4) | 0.84086 (15) | 0.12911 (11) | 0.0375 (7) | |
H47A | 0.3152 | 0.8223 | 0.1561 | 0.045* | |
H47B | 0.2737 | 0.8581 | 0.1097 | 0.045* | |
C48 | 0.4734 (4) | 0.78160 (13) | 0.10597 (9) | 0.0295 (6) | |
H48 | 0.6035 | 0.7772 | 0.1181 | 0.035* | |
C49 | 0.4846 (4) | 0.78635 (14) | 0.05643 (9) | 0.0300 (6) | |
O50 | 0.5207 (3) | 0.83844 (10) | 0.03534 (7) | 0.0404 (5) | |
N51 | 0.4441 (4) | 0.72297 (12) | 0.03941 (7) | 0.0320 (6) | |
C52 | 0.4636 (6) | 0.70676 (17) | −0.00714 (9) | 0.0450 (8) | |
H52A | 0.4556 | 0.7497 | −0.0244 | 0.068* | |
H52B | 0.3628 | 0.6751 | −0.0161 | 0.068* | |
H52C | 0.5856 | 0.6846 | −0.0123 | 0.068* | |
C53 | 0.4100 (4) | 0.66876 (14) | 0.07240 (9) | 0.0294 (6) | |
C54 | 0.2379 (5) | 0.62580 (15) | 0.06236 (10) | 0.0367 (7) | |
H54A | 0.1332 | 0.6566 | 0.0548 | 0.055* | |
H54B | 0.2044 | 0.5981 | 0.0883 | 0.055* | |
H54C | 0.2643 | 0.5948 | 0.0375 | 0.055* | |
C55 | 0.5835 (5) | 0.62492 (16) | 0.08050 (10) | 0.0404 (8) | |
H55A | 0.6200 | 0.6016 | 0.0531 | 0.061* | |
H55B | 0.5562 | 0.5900 | 0.1031 | 0.061* | |
H55C | 0.6865 | 0.6548 | 0.0905 | 0.061* | |
N56 | 0.3730 (4) | 0.71421 (12) | 0.11235 (8) | 0.0276 (5) | |
H56A | 0.411 (4) | 0.6939 (14) | 0.1374 (7) | 0.041 (4)* | |
H56B | 0.254 (3) | 0.7225 (16) | 0.1151 (11) | 0.041 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0272 (4) | 0.0518 (4) | 0.0288 (3) | −0.0009 (3) | −0.0003 (3) | 0.0016 (3) |
Cl2 | 0.0310 (4) | 0.0531 (4) | 0.0270 (3) | 0.0020 (4) | 0.0009 (3) | −0.0046 (3) |
Cl3 | 0.0247 (3) | 0.0557 (4) | 0.0265 (3) | −0.0007 (4) | 0.0009 (3) | 0.0008 (3) |
C1 | 0.059 (2) | 0.0333 (16) | 0.0443 (19) | −0.0063 (16) | 0.0077 (18) | −0.0072 (14) |
C2 | 0.084 (3) | 0.0417 (19) | 0.050 (2) | −0.018 (2) | 0.013 (2) | −0.0044 (17) |
C3 | 0.107 (4) | 0.0432 (19) | 0.0409 (19) | −0.017 (2) | −0.008 (2) | 0.0042 (16) |
C4 | 0.081 (3) | 0.0426 (18) | 0.0457 (19) | −0.009 (2) | −0.020 (2) | 0.0036 (15) |
C5 | 0.065 (3) | 0.0361 (16) | 0.0408 (18) | −0.0084 (18) | −0.0093 (18) | −0.0002 (13) |
C6 | 0.057 (2) | 0.0226 (13) | 0.0328 (16) | −0.0054 (14) | 0.0020 (16) | −0.0085 (11) |
C7 | 0.0360 (18) | 0.0343 (15) | 0.0355 (16) | 0.0001 (13) | 0.0001 (14) | −0.0054 (12) |
C8 | 0.0308 (15) | 0.0293 (13) | 0.0277 (13) | 0.0007 (13) | −0.0006 (13) | −0.0030 (10) |
C9 | 0.0289 (15) | 0.0352 (14) | 0.0292 (13) | 0.0017 (13) | 0.0014 (14) | −0.0019 (11) |
O10 | 0.0555 (17) | 0.0432 (11) | 0.0324 (11) | 0.0009 (11) | 0.0096 (11) | −0.0089 (9) |
N11 | 0.0343 (15) | 0.0345 (12) | 0.0236 (11) | 0.0040 (11) | 0.0013 (11) | −0.0021 (9) |
C12 | 0.047 (2) | 0.0460 (16) | 0.0244 (14) | 0.0049 (16) | −0.0004 (14) | 0.0041 (12) |
C13 | 0.0381 (19) | 0.0295 (13) | 0.0236 (13) | 0.0024 (12) | −0.0016 (13) | 0.0002 (11) |
C14 | 0.047 (2) | 0.0392 (16) | 0.0382 (17) | −0.0080 (16) | −0.0041 (15) | 0.0017 (13) |
C15 | 0.053 (2) | 0.0396 (16) | 0.0288 (16) | 0.0134 (16) | 0.0028 (15) | −0.0028 (13) |
N16 | 0.0302 (14) | 0.0329 (12) | 0.0242 (12) | 0.0002 (11) | −0.0013 (11) | −0.0021 (9) |
C21 | 0.050 (2) | 0.0419 (17) | 0.0403 (18) | 0.0053 (16) | −0.0040 (17) | 0.0007 (14) |
C22 | 0.056 (2) | 0.0375 (17) | 0.051 (2) | 0.0090 (17) | 0.0115 (18) | 0.0010 (15) |
C23 | 0.076 (3) | 0.0262 (15) | 0.0389 (18) | −0.0030 (16) | 0.0091 (19) | −0.0045 (13) |
C24 | 0.071 (3) | 0.0408 (17) | 0.0382 (17) | −0.0108 (18) | −0.0092 (19) | −0.0041 (14) |
C25 | 0.046 (2) | 0.0382 (16) | 0.0400 (18) | −0.0033 (15) | −0.0046 (16) | 0.0008 (14) |
C26 | 0.0428 (17) | 0.0248 (12) | 0.0307 (14) | −0.0050 (13) | −0.0010 (15) | 0.0002 (11) |
C27 | 0.0325 (17) | 0.0348 (15) | 0.0314 (15) | −0.0010 (13) | 0.0014 (13) | 0.0014 (12) |
C28 | 0.0286 (16) | 0.0322 (14) | 0.0287 (13) | 0.0035 (12) | 0.0004 (12) | −0.0004 (11) |
C29 | 0.0255 (14) | 0.0394 (15) | 0.0262 (13) | 0.0046 (13) | 0.0008 (13) | −0.0022 (11) |
O30 | 0.0445 (15) | 0.0467 (11) | 0.0300 (10) | 0.0116 (11) | −0.0034 (10) | 0.0045 (9) |
N31 | 0.0329 (15) | 0.0376 (12) | 0.0219 (11) | 0.0041 (11) | −0.0015 (10) | −0.0022 (9) |
C32 | 0.048 (2) | 0.0441 (16) | 0.0289 (15) | 0.0060 (16) | −0.0036 (15) | −0.0099 (12) |
C33 | 0.0322 (18) | 0.0325 (14) | 0.0269 (14) | 0.0013 (12) | 0.0028 (12) | −0.0041 (11) |
C34 | 0.041 (2) | 0.0436 (17) | 0.0387 (17) | −0.0109 (15) | 0.0086 (15) | −0.0086 (14) |
C35 | 0.047 (2) | 0.0367 (16) | 0.0317 (16) | 0.0067 (15) | −0.0011 (14) | 0.0058 (13) |
N36 | 0.0280 (14) | 0.0362 (13) | 0.0236 (11) | −0.0022 (11) | 0.0021 (11) | −0.0001 (10) |
C41 | 0.0406 (19) | 0.0456 (18) | 0.0365 (17) | −0.0084 (15) | 0.0090 (16) | −0.0055 (14) |
C42 | 0.043 (2) | 0.0448 (18) | 0.0380 (17) | −0.0148 (15) | 0.0021 (15) | 0.0043 (14) |
C43 | 0.051 (2) | 0.0307 (16) | 0.053 (2) | −0.0063 (16) | −0.0079 (18) | −0.0005 (15) |
C44 | 0.058 (3) | 0.0424 (19) | 0.078 (3) | −0.0053 (19) | 0.017 (2) | −0.0264 (18) |
C45 | 0.042 (2) | 0.0409 (17) | 0.063 (2) | −0.0044 (15) | 0.0148 (18) | −0.0093 (16) |
C46 | 0.0354 (19) | 0.0287 (13) | 0.0321 (14) | −0.0010 (12) | −0.0002 (13) | 0.0030 (11) |
C47 | 0.0325 (17) | 0.0378 (16) | 0.0422 (17) | −0.0061 (14) | 0.0073 (15) | −0.0073 (13) |
C48 | 0.0234 (15) | 0.0353 (14) | 0.0297 (13) | −0.0021 (13) | 0.0002 (13) | −0.0011 (11) |
C49 | 0.0248 (17) | 0.0345 (14) | 0.0306 (14) | −0.0005 (12) | 0.0003 (12) | 0.0019 (11) |
O50 | 0.0455 (14) | 0.0366 (10) | 0.0390 (11) | −0.0050 (10) | 0.0076 (11) | 0.0073 (9) |
N51 | 0.0350 (15) | 0.0361 (12) | 0.0249 (11) | −0.0053 (11) | 0.0019 (11) | 0.0007 (9) |
C52 | 0.054 (2) | 0.0530 (18) | 0.0279 (14) | −0.0115 (18) | 0.0053 (17) | −0.0044 (13) |
C53 | 0.0299 (16) | 0.0324 (14) | 0.0260 (14) | −0.0002 (12) | −0.0013 (12) | 0.0003 (11) |
C54 | 0.0379 (19) | 0.0340 (15) | 0.0383 (17) | −0.0061 (14) | −0.0032 (14) | 0.0033 (13) |
C55 | 0.038 (2) | 0.0415 (16) | 0.0417 (17) | 0.0099 (15) | −0.0024 (15) | −0.0028 (14) |
N56 | 0.0241 (13) | 0.0320 (12) | 0.0267 (12) | 0.0012 (10) | 0.0004 (11) | 0.0040 (9) |
C1—C6 | 1.384 (5) | C29—O30 | 1.219 (3) |
C1—C2 | 1.387 (5) | C29—N31 | 1.339 (3) |
C1—H1 | 0.9500 | N31—C32 | 1.461 (3) |
C2—C3 | 1.377 (6) | N31—C33 | 1.471 (3) |
C2—H2 | 0.9500 | C32—H32A | 0.9800 |
C3—C4 | 1.373 (6) | C32—H32B | 0.9800 |
C3—H3 | 0.9500 | C32—H32C | 0.9800 |
C4—C5 | 1.386 (4) | C33—C35 | 1.506 (4) |
C4—H4 | 0.9500 | C33—C34 | 1.514 (4) |
C5—C6 | 1.384 (5) | C33—N36 | 1.514 (4) |
C5—H5 | 0.9500 | C34—H34A | 0.9800 |
C6—C7 | 1.520 (4) | C34—H34B | 0.9800 |
C7—C8 | 1.522 (4) | C34—H34C | 0.9800 |
C7—H7A | 0.9900 | C35—H35A | 0.9800 |
C7—H7B | 0.9900 | C35—H35B | 0.9800 |
C8—N16 | 1.495 (3) | C35—H35C | 0.9800 |
C8—C9 | 1.526 (4) | N36—H36A | 0.872 (17) |
C8—H8 | 1.0000 | N36—H36B | 0.883 (18) |
C9—O10 | 1.219 (3) | C41—C46 | 1.376 (4) |
C9—N11 | 1.339 (3) | C41—C42 | 1.383 (4) |
N11—C12 | 1.448 (3) | C41—H41 | 0.9500 |
N11—C13 | 1.473 (3) | C42—C43 | 1.359 (5) |
C12—H12A | 0.9800 | C42—H42 | 0.9500 |
C12—H12B | 0.9800 | C43—C44 | 1.378 (5) |
C12—H12C | 0.9800 | C43—H43 | 0.9500 |
C13—C15 | 1.501 (4) | C44—C45 | 1.375 (5) |
C13—C14 | 1.517 (4) | C44—H44 | 0.9500 |
C13—N16 | 1.517 (4) | C45—C46 | 1.391 (4) |
C14—H14A | 0.9800 | C45—H45 | 0.9500 |
C14—H14B | 0.9800 | C46—C47 | 1.514 (4) |
C14—H14C | 0.9800 | C47—C48 | 1.510 (4) |
C15—H15A | 0.9800 | C47—H47A | 0.9900 |
C15—H15B | 0.9800 | C47—H47B | 0.9900 |
C15—H15C | 0.9800 | C48—N56 | 1.493 (4) |
N16—H16A | 0.867 (18) | C48—C49 | 1.510 (4) |
N16—H16B | 0.872 (17) | C48—H48 | 1.0000 |
C21—C22 | 1.375 (4) | C49—O50 | 1.217 (3) |
C21—C26 | 1.390 (5) | C49—N51 | 1.355 (3) |
C21—H21 | 0.9500 | N51—C52 | 1.454 (3) |
C22—C23 | 1.369 (5) | N51—C53 | 1.466 (3) |
C22—H22 | 0.9500 | C52—H52A | 0.9800 |
C23—C24 | 1.365 (5) | C52—H52B | 0.9800 |
C23—H23 | 0.9500 | C52—H52C | 0.9800 |
C24—C25 | 1.380 (5) | C53—C54 | 1.509 (4) |
C24—H24 | 0.9500 | C53—C55 | 1.515 (4) |
C25—C26 | 1.374 (4) | C53—N56 | 1.518 (4) |
C25—H25 | 0.9500 | C54—H54A | 0.9800 |
C26—C27 | 1.513 (4) | C54—H54B | 0.9800 |
C27—C28 | 1.527 (4) | C54—H54C | 0.9800 |
C27—H27A | 0.9900 | C55—H55A | 0.9800 |
C27—H27B | 0.9900 | C55—H55B | 0.9800 |
C28—N36 | 1.502 (4) | C55—H55C | 0.9800 |
C28—C29 | 1.523 (4) | N56—H56A | 0.895 (17) |
C28—H28 | 1.0000 | N56—H56B | 0.868 (18) |
C6—C1—C2 | 120.6 (4) | C29—N31—C32 | 122.4 (2) |
C6—C1—H1 | 119.7 | C29—N31—C33 | 114.5 (2) |
C2—C1—H1 | 119.7 | C32—N31—C33 | 121.8 (2) |
C3—C2—C1 | 119.9 (4) | N31—C32—H32A | 109.5 |
C3—C2—H2 | 120.0 | N31—C32—H32B | 109.5 |
C1—C2—H2 | 120.0 | H32A—C32—H32B | 109.5 |
C4—C3—C2 | 119.8 (3) | N31—C32—H32C | 109.5 |
C4—C3—H3 | 120.1 | H32A—C32—H32C | 109.5 |
C2—C3—H3 | 120.1 | H32B—C32—H32C | 109.5 |
C3—C4—C5 | 120.5 (4) | N31—C33—C35 | 112.8 (2) |
C3—C4—H4 | 119.7 | N31—C33—C34 | 111.6 (2) |
C5—C4—H4 | 119.7 | C35—C33—C34 | 112.3 (2) |
C6—C5—C4 | 120.2 (4) | N31—C33—N36 | 99.9 (2) |
C6—C5—H5 | 119.9 | C35—C33—N36 | 109.6 (2) |
C4—C5—H5 | 119.9 | C34—C33—N36 | 110.0 (2) |
C1—C6—C5 | 118.9 (3) | C33—C34—H34A | 109.5 |
C1—C6—C7 | 118.6 (3) | C33—C34—H34B | 109.5 |
C5—C6—C7 | 122.0 (3) | H34A—C34—H34B | 109.5 |
C6—C7—C8 | 118.3 (2) | C33—C34—H34C | 109.5 |
C6—C7—H7A | 107.7 | H34A—C34—H34C | 109.5 |
C8—C7—H7A | 107.7 | H34B—C34—H34C | 109.5 |
C6—C7—H7B | 107.7 | C33—C35—H35A | 109.5 |
C8—C7—H7B | 107.7 | C33—C35—H35B | 109.5 |
H7A—C7—H7B | 107.1 | H35A—C35—H35B | 109.5 |
N16—C8—C7 | 115.2 (2) | C33—C35—H35C | 109.5 |
N16—C8—C9 | 101.9 (2) | H35A—C35—H35C | 109.5 |
C7—C8—C9 | 109.0 (2) | H35B—C35—H35C | 109.5 |
N16—C8—H8 | 110.1 | C28—N36—C33 | 107.1 (2) |
C7—C8—H8 | 110.1 | C28—N36—H36A | 110 (2) |
C9—C8—H8 | 110.1 | C33—N36—H36A | 111 (2) |
O10—C9—N11 | 126.6 (3) | C28—N36—H36B | 107 (2) |
O10—C9—C8 | 124.9 (2) | C33—N36—H36B | 108 (2) |
N11—C9—C8 | 108.5 (2) | H36A—N36—H36B | 113 (3) |
C9—N11—C12 | 122.5 (2) | C46—C41—C42 | 120.8 (3) |
C9—N11—C13 | 114.1 (2) | C46—C41—H41 | 119.6 |
C12—N11—C13 | 121.9 (2) | C42—C41—H41 | 119.6 |
N11—C12—H12A | 109.5 | C43—C42—C41 | 121.1 (3) |
N11—C12—H12B | 109.5 | C43—C42—H42 | 119.4 |
H12A—C12—H12B | 109.5 | C41—C42—H42 | 119.4 |
N11—C12—H12C | 109.5 | C42—C43—C44 | 118.6 (3) |
H12A—C12—H12C | 109.5 | C42—C43—H43 | 120.7 |
H12B—C12—H12C | 109.5 | C44—C43—H43 | 120.7 |
N11—C13—C15 | 112.5 (2) | C45—C44—C43 | 121.1 (3) |
N11—C13—C14 | 110.5 (2) | C45—C44—H44 | 119.5 |
C15—C13—C14 | 113.3 (2) | C43—C44—H44 | 119.5 |
N11—C13—N16 | 99.9 (2) | C44—C45—C46 | 120.4 (3) |
C15—C13—N16 | 109.1 (2) | C44—C45—H45 | 119.8 |
C14—C13—N16 | 110.8 (2) | C46—C45—H45 | 119.8 |
C13—C14—H14A | 109.5 | C41—C46—C45 | 118.0 (3) |
C13—C14—H14B | 109.5 | C41—C46—C47 | 124.2 (3) |
H14A—C14—H14B | 109.5 | C45—C46—C47 | 117.7 (3) |
C13—C14—H14C | 109.5 | C48—C47—C46 | 116.3 (3) |
H14A—C14—H14C | 109.5 | C48—C47—H47A | 108.2 |
H14B—C14—H14C | 109.5 | C46—C47—H47A | 108.2 |
C13—C15—H15A | 109.5 | C48—C47—H47B | 108.2 |
C13—C15—H15B | 109.5 | C46—C47—H47B | 108.2 |
H15A—C15—H15B | 109.5 | H47A—C47—H47B | 107.4 |
C13—C15—H15C | 109.5 | N56—C48—C49 | 102.0 (2) |
H15A—C15—H15C | 109.5 | N56—C48—C47 | 112.0 (2) |
H15B—C15—H15C | 109.5 | C49—C48—C47 | 116.3 (2) |
C8—N16—C13 | 107.5 (2) | N56—C48—H48 | 108.8 |
C8—N16—H16A | 108 (2) | C49—C48—H48 | 108.8 |
C13—N16—H16A | 109 (2) | C47—C48—H48 | 108.8 |
C8—N16—H16B | 119 (2) | O50—C49—N51 | 125.8 (3) |
C13—N16—H16B | 110 (2) | O50—C49—C48 | 125.8 (3) |
H16A—N16—H16B | 104 (3) | N51—C49—C48 | 108.3 (2) |
C22—C21—C26 | 120.7 (3) | C49—N51—C52 | 122.9 (2) |
C22—C21—H21 | 119.6 | C49—N51—C53 | 114.5 (2) |
C26—C21—H21 | 119.6 | C52—N51—C53 | 121.8 (2) |
C23—C22—C21 | 119.7 (4) | N51—C52—H52A | 109.5 |
C23—C22—H22 | 120.1 | N51—C52—H52B | 109.5 |
C21—C22—H22 | 120.1 | H52A—C52—H52B | 109.5 |
C24—C23—C22 | 120.4 (3) | N51—C52—H52C | 109.5 |
C24—C23—H23 | 119.8 | H52A—C52—H52C | 109.5 |
C22—C23—H23 | 119.8 | H52B—C52—H52C | 109.5 |
C23—C24—C25 | 119.9 (3) | N51—C53—C54 | 112.7 (2) |
C23—C24—H24 | 120.1 | N51—C53—C55 | 111.8 (2) |
C25—C24—H24 | 120.1 | C54—C53—C55 | 112.9 (2) |
C26—C25—C24 | 120.8 (3) | N51—C53—N56 | 99.5 (2) |
C26—C25—H25 | 119.6 | C54—C53—N56 | 109.6 (2) |
C24—C25—H25 | 119.6 | C55—C53—N56 | 109.4 (2) |
C25—C26—C21 | 118.4 (3) | C53—C54—H54A | 109.5 |
C25—C26—C27 | 120.6 (3) | C53—C54—H54B | 109.5 |
C21—C26—C27 | 121.0 (3) | H54A—C54—H54B | 109.5 |
C26—C27—C28 | 113.6 (2) | C53—C54—H54C | 109.5 |
C26—C27—H27A | 108.9 | H54A—C54—H54C | 109.5 |
C28—C27—H27A | 108.9 | H54B—C54—H54C | 109.5 |
C26—C27—H27B | 108.9 | C53—C55—H55A | 109.5 |
C28—C27—H27B | 108.9 | C53—C55—H55B | 109.5 |
H27A—C27—H27B | 107.7 | H55A—C55—H55B | 109.5 |
N36—C28—C29 | 101.3 (2) | C53—C55—H55C | 109.5 |
N36—C28—C27 | 114.1 (2) | H55A—C55—H55C | 109.5 |
C29—C28—C27 | 113.6 (2) | H55B—C55—H55C | 109.5 |
N36—C28—H28 | 109.2 | C48—N56—C53 | 108.3 (2) |
C29—C28—H28 | 109.2 | C48—N56—H56A | 110 (2) |
C27—C28—H28 | 109.2 | C53—N56—H56A | 112 (2) |
O30—C29—N31 | 127.0 (2) | C48—N56—H56B | 109 (2) |
O30—C29—C28 | 124.8 (2) | C53—N56—H56B | 111 (2) |
N31—C29—C28 | 108.2 (2) | H56A—N56—H56B | 107 (3) |
C13H19N2O+·Cl− | F(000) = 1632 |
Mr = 254.75 | Dx = 1.220 Mg m−3 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.69040 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3066 reflections |
a = 7.123 (1) Å | θ = 2.7–23.6° |
b = 19.232 (3) Å | µ = 0.26 mm−1 |
c = 30.384 (4) Å | T = 150 K |
V = 4162.3 (10) Å3 | Block, colourless |
Z = 12 | 0.2 × 0.06 × 0.04 mm |
Bruker D8 diffractometer | 13171 independent reflections |
Radiation source: Daresbury SRS, Station 16.2SMX | 8896 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.126 |
ω rotation with narrow frame scans | θmax = 30.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.949, Tmax = 0.990 | k = −27→27 |
48955 measured reflections | l = −43→43 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.171 | w = 1/[σ2(Fo2) + (0.0126P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
13171 reflections | Δρmax = 0.46 e Å−3 |
488 parameters | Δρmin = −0.32 e Å−3 |
6 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.09 (6) |
C13H19N2O+·Cl− | V = 4162.3 (10) Å3 |
Mr = 254.75 | Z = 12 |
Orthorhombic, P212121 | Synchrotron radiation, λ = 0.69040 Å |
a = 7.123 (1) Å | µ = 0.26 mm−1 |
b = 19.232 (3) Å | T = 150 K |
c = 30.384 (4) Å | 0.2 × 0.06 × 0.04 mm |
Bruker D8 diffractometer | 13171 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 8896 reflections with I > 2σ(I) |
Tmin = 0.949, Tmax = 0.990 | Rint = 0.126 |
48955 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.171 | Δρmax = 0.46 e Å−3 |
S = 1.03 | Δρmin = −0.32 e Å−3 |
13171 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
488 parameters | Absolute structure parameter: 0.09 (6) |
6 restraints |
Experimental. A correction to account for beam decay and absorption was applied using SADABS. The ratio of max to min apparent transmission was 0.739. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.53380 (11) | 0.32275 (4) | 0.79074 (2) | 0.03396 (16) | |
Cl2 | 0.96381 (13) | 0.70284 (4) | 0.96122 (2) | 0.03500 (17) | |
Cl3 | 0.04468 (11) | 0.25258 (4) | 0.87330 (2) | 0.03409 (17) | |
H56A | 0.600 (5) | 0.3032 (16) | 0.8612 (7) | 0.036 (4)* | |
H56B | 0.746 (3) | 0.2736 (17) | 0.8869 (11) | 0.036 (4)* | |
C1 | 0.2282 (6) | 0.53542 (17) | 0.98777 (11) | 0.0430 (8) | |
H1 | 0.1076 | 0.5456 | 0.9760 | 0.052* | |
C2 | 0.2455 (7) | 0.4905 (2) | 1.02394 (13) | 0.0560 (11) | |
H2 | 0.1364 | 0.4703 | 1.0367 | 0.067* | |
C3 | 0.4205 (8) | 0.47542 (19) | 1.04115 (12) | 0.0622 (13) | |
H3 | 0.4319 | 0.4443 | 1.0653 | 0.075* | |
C4 | 0.5774 (7) | 0.50544 (18) | 1.02342 (12) | 0.0539 (11) | |
H4 | 0.6975 | 0.4958 | 1.0357 | 0.065* | |
C5 | 0.5619 (6) | 0.54990 (17) | 0.98758 (11) | 0.0422 (8) | |
H5 | 0.6716 | 0.5703 | 0.9753 | 0.051* | |
C6 | 0.3866 (5) | 0.56480 (15) | 0.96944 (10) | 0.0349 (7) | |
C7 | 0.3667 (5) | 0.60562 (15) | 0.92724 (10) | 0.0318 (7) | |
H7A | 0.2317 | 0.6164 | 0.9233 | 0.038* | |
H7B | 0.4037 | 0.5747 | 0.9027 | 0.038* | |
C8 | 0.4754 (5) | 0.67320 (14) | 0.92214 (9) | 0.0276 (6) | |
H8 | 0.6082 | 0.6665 | 0.9320 | 0.033* | |
C9 | 0.4718 (4) | 0.69630 (15) | 0.87405 (9) | 0.0306 (6) | |
O10 | 0.4953 (4) | 0.65743 (11) | 0.84275 (7) | 0.0407 (6) | |
N11 | 0.4343 (4) | 0.76402 (12) | 0.87275 (8) | 0.0293 (5) | |
C12 | 0.4476 (5) | 0.80409 (18) | 0.83224 (9) | 0.0381 (8) | |
H12A | 0.4357 | 0.7728 | 0.8069 | 0.057* | |
H12B | 0.5695 | 0.8277 | 0.8311 | 0.057* | |
H12C | 0.3466 | 0.8387 | 0.8314 | 0.057* | |
C13 | 0.4273 (5) | 0.79772 (15) | 0.91599 (9) | 0.0292 (6) | |
C14 | 0.6154 (5) | 0.83084 (18) | 0.92734 (11) | 0.0407 (8) | |
H14A | 0.6439 | 0.8675 | 0.9060 | 0.061* | |
H14B | 0.7143 | 0.7954 | 0.9264 | 0.061* | |
H14C | 0.6093 | 0.8509 | 0.9570 | 0.061* | |
C15 | 0.2643 (5) | 0.84718 (17) | 0.92033 (10) | 0.0393 (8) | |
H15A | 0.1487 | 0.8240 | 0.9107 | 0.059* | |
H15B | 0.2868 | 0.8882 | 0.9019 | 0.059* | |
H15C | 0.2514 | 0.8615 | 0.9512 | 0.059* | |
N16 | 0.3922 (4) | 0.73451 (13) | 0.94478 (8) | 0.0275 (5) | |
H16A | 0.272 (3) | 0.7298 (18) | 0.9466 (11) | 0.036 (4)* | |
H16B | 0.421 (5) | 0.7438 (16) | 0.9719 (7) | 0.036 (4)* | |
C21 | −0.1484 (5) | 0.47847 (18) | 0.79588 (11) | 0.0409 (8) | |
H21 | −0.2260 | 0.4742 | 0.7706 | 0.049* | |
C22 | −0.2146 (6) | 0.51350 (18) | 0.83248 (12) | 0.0475 (9) | |
H22 | −0.3371 | 0.5331 | 0.8322 | 0.057* | |
C23 | −0.1043 (6) | 0.52008 (17) | 0.86910 (12) | 0.0478 (10) | |
H23 | −0.1486 | 0.5455 | 0.8938 | 0.057* | |
C24 | 0.0712 (6) | 0.48976 (18) | 0.87013 (11) | 0.0472 (9) | |
H24 | 0.1459 | 0.4925 | 0.8960 | 0.057* | |
C25 | 0.1383 (5) | 0.45512 (17) | 0.83318 (10) | 0.0388 (8) | |
H25 | 0.2603 | 0.4351 | 0.8337 | 0.047* | |
C26 | 0.0300 (5) | 0.44944 (14) | 0.79575 (9) | 0.0321 (6) | |
C27 | 0.1026 (5) | 0.41159 (15) | 0.75596 (9) | 0.0321 (7) | |
H27A | 0.2407 | 0.4071 | 0.7585 | 0.039* | |
H27B | 0.0759 | 0.4400 | 0.7295 | 0.039* | |
C28 | 0.0186 (4) | 0.33942 (14) | 0.74938 (9) | 0.0274 (6) | |
H28 | −0.1171 | 0.3406 | 0.7579 | 0.033* | |
C29 | 0.0348 (5) | 0.31232 (15) | 0.70267 (9) | 0.0302 (6) | |
O30 | 0.0128 (4) | 0.34709 (12) | 0.66958 (7) | 0.0404 (6) | |
N31 | 0.0729 (4) | 0.24400 (13) | 0.70432 (7) | 0.0289 (5) | |
C32 | 0.0578 (6) | 0.19817 (18) | 0.66614 (10) | 0.0395 (8) | |
H32A | 0.0584 | 0.2261 | 0.6391 | 0.059* | |
H32B | −0.0597 | 0.1717 | 0.6679 | 0.059* | |
H32C | 0.1644 | 0.1660 | 0.6658 | 0.059* | |
C33 | 0.0869 (4) | 0.21537 (15) | 0.74915 (9) | 0.0277 (6) | |
C34 | −0.0947 (5) | 0.18070 (18) | 0.76337 (11) | 0.0390 (8) | |
H34A | −0.1230 | 0.1420 | 0.7434 | 0.059* | |
H34B | −0.1973 | 0.2146 | 0.7624 | 0.059* | |
H34C | −0.0810 | 0.1630 | 0.7935 | 0.059* | |
C35 | 0.2567 (5) | 0.16925 (17) | 0.75526 (10) | 0.0360 (7) | |
H35A | 0.3698 | 0.1942 | 0.7458 | 0.054* | |
H35B | 0.2420 | 0.1270 | 0.7375 | 0.054* | |
H35C | 0.2686 | 0.1566 | 0.7864 | 0.054* | |
N36 | 0.1146 (4) | 0.28279 (13) | 0.77481 (8) | 0.0265 (5) | |
H36A | 0.080 (5) | 0.2829 (17) | 0.8024 (6) | 0.036 (4)* | |
H36B | 0.236 (3) | 0.2922 (18) | 0.7749 (11) | 0.036 (4)* | |
C41 | 0.3222 (5) | 0.08721 (18) | 0.87222 (11) | 0.0381 (7) | |
H41 | 0.2695 | 0.1186 | 0.8930 | 0.046* | |
C42 | 0.2153 (5) | 0.03171 (17) | 0.85695 (11) | 0.0392 (8) | |
H42 | 0.0906 | 0.0256 | 0.8674 | 0.047* | |
C43 | 0.2876 (6) | −0.01399 (18) | 0.82713 (12) | 0.0434 (8) | |
H43 | 0.2141 | −0.0518 | 0.8167 | 0.052* | |
C44 | 0.4680 (6) | −0.00467 (18) | 0.81235 (14) | 0.0553 (10) | |
H44 | 0.5198 | −0.0362 | 0.7915 | 0.066* | |
C45 | 0.5744 (6) | 0.05022 (18) | 0.82757 (12) | 0.0463 (9) | |
H45 | 0.6994 | 0.0558 | 0.8172 | 0.056* | |
C46 | 0.5030 (4) | 0.09731 (15) | 0.85769 (9) | 0.0297 (7) | |
C47 | 0.6257 (4) | 0.15824 (16) | 0.87117 (11) | 0.0345 (7) | |
H47A | 0.7253 | 0.1407 | 0.8910 | 0.041* | |
H47B | 0.6883 | 0.1766 | 0.8445 | 0.041* | |
C48 | 0.5267 (4) | 0.21795 (14) | 0.89394 (9) | 0.0260 (6) | |
H48 | 0.3965 | 0.2223 | 0.8818 | 0.031* | |
C49 | 0.5162 (4) | 0.21312 (15) | 0.94358 (9) | 0.0286 (6) | |
O50 | 0.4780 (4) | 0.16091 (11) | 0.96445 (7) | 0.0391 (5) | |
N51 | 0.5560 (4) | 0.27634 (13) | 0.96047 (8) | 0.0307 (6) | |
C52 | 0.5372 (6) | 0.29278 (18) | 1.00678 (9) | 0.0425 (8) | |
H52A | 0.5478 | 0.2501 | 1.0242 | 0.064* | |
H52B | 0.4143 | 0.3142 | 1.0121 | 0.064* | |
H52C | 0.6367 | 0.3252 | 1.0155 | 0.064* | |
C53 | 0.5908 (4) | 0.33055 (15) | 0.92720 (9) | 0.0291 (6) | |
C54 | 0.7626 (5) | 0.37387 (16) | 0.93720 (10) | 0.0350 (7) | |
H54A | 0.8699 | 0.3432 | 0.9427 | 0.053* | |
H54B | 0.7388 | 0.4025 | 0.9633 | 0.053* | |
H54C | 0.7903 | 0.4041 | 0.9120 | 0.053* | |
C55 | 0.4180 (5) | 0.37474 (18) | 0.91928 (11) | 0.0388 (8) | |
H55A | 0.3822 | 0.3980 | 0.9467 | 0.058* | |
H55B | 0.3145 | 0.3451 | 0.9093 | 0.058* | |
H55C | 0.4456 | 0.4097 | 0.8967 | 0.058* | |
N56 | 0.6276 (4) | 0.28507 (13) | 0.88767 (8) | 0.0268 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0249 (3) | 0.0500 (4) | 0.0270 (3) | −0.0013 (3) | 0.0001 (3) | 0.0018 (3) |
Cl2 | 0.0294 (4) | 0.0500 (4) | 0.0256 (3) | 0.0017 (4) | 0.0005 (3) | −0.0043 (3) |
Cl3 | 0.0227 (3) | 0.0542 (4) | 0.0255 (3) | −0.0003 (4) | 0.0005 (3) | 0.0001 (3) |
C1 | 0.055 (2) | 0.0341 (17) | 0.0397 (18) | −0.0077 (17) | 0.0087 (17) | −0.0059 (14) |
C2 | 0.083 (3) | 0.041 (2) | 0.044 (2) | −0.018 (2) | 0.017 (2) | −0.0034 (17) |
C3 | 0.111 (4) | 0.0370 (19) | 0.0382 (19) | −0.015 (2) | −0.008 (2) | 0.0027 (16) |
C4 | 0.075 (3) | 0.0396 (19) | 0.047 (2) | −0.008 (2) | −0.020 (2) | 0.0037 (16) |
C5 | 0.053 (2) | 0.0363 (17) | 0.0377 (17) | −0.0046 (17) | −0.0051 (17) | −0.0020 (14) |
C6 | 0.052 (2) | 0.0253 (14) | 0.0276 (15) | −0.0024 (14) | 0.0008 (14) | −0.0065 (11) |
C7 | 0.0313 (17) | 0.0304 (15) | 0.0337 (15) | 0.0000 (13) | 0.0005 (13) | −0.0079 (12) |
C8 | 0.0277 (14) | 0.0297 (13) | 0.0254 (13) | 0.0038 (13) | −0.0010 (12) | −0.0041 (11) |
C9 | 0.0274 (14) | 0.0369 (15) | 0.0274 (13) | 0.0029 (13) | 0.0029 (13) | −0.0030 (12) |
O10 | 0.0510 (16) | 0.0409 (12) | 0.0303 (10) | 0.0025 (11) | 0.0109 (10) | −0.0086 (9) |
N11 | 0.0337 (14) | 0.0302 (12) | 0.0239 (11) | 0.0045 (11) | 0.0008 (11) | −0.0002 (9) |
C12 | 0.044 (2) | 0.0492 (18) | 0.0208 (13) | 0.0078 (17) | 0.0034 (14) | 0.0036 (13) |
C13 | 0.0391 (19) | 0.0285 (14) | 0.0201 (12) | 0.0009 (13) | 0.0010 (12) | −0.0001 (11) |
C14 | 0.046 (2) | 0.0391 (18) | 0.0367 (17) | −0.0075 (16) | −0.0032 (15) | 0.0015 (14) |
C15 | 0.051 (2) | 0.0377 (17) | 0.0293 (16) | 0.0155 (16) | 0.0048 (15) | −0.0004 (14) |
N16 | 0.0312 (14) | 0.0302 (12) | 0.0210 (11) | 0.0003 (11) | −0.0023 (10) | −0.0028 (10) |
C21 | 0.042 (2) | 0.0428 (18) | 0.0376 (18) | 0.0071 (16) | −0.0056 (16) | −0.0002 (15) |
C22 | 0.057 (3) | 0.0360 (18) | 0.050 (2) | 0.0088 (18) | 0.0107 (19) | 0.0017 (16) |
C23 | 0.081 (3) | 0.0271 (16) | 0.0355 (17) | −0.0012 (18) | 0.0136 (19) | −0.0033 (14) |
C24 | 0.069 (3) | 0.0414 (18) | 0.0315 (16) | −0.0119 (19) | −0.0065 (18) | −0.0055 (14) |
C25 | 0.045 (2) | 0.0359 (16) | 0.0356 (17) | −0.0053 (15) | −0.0066 (15) | −0.0022 (14) |
C26 | 0.0402 (17) | 0.0254 (13) | 0.0306 (14) | −0.0033 (13) | −0.0011 (14) | 0.0029 (11) |
C27 | 0.0308 (16) | 0.0355 (16) | 0.0300 (15) | −0.0063 (13) | 0.0002 (13) | 0.0028 (12) |
C28 | 0.0234 (14) | 0.0325 (14) | 0.0262 (13) | 0.0042 (12) | −0.0019 (11) | −0.0024 (11) |
C29 | 0.0252 (14) | 0.0369 (15) | 0.0285 (14) | 0.0042 (13) | −0.0037 (12) | −0.0010 (12) |
O30 | 0.0482 (16) | 0.0446 (12) | 0.0284 (10) | 0.0123 (11) | −0.0047 (10) | 0.0039 (9) |
N31 | 0.0313 (14) | 0.0341 (12) | 0.0213 (11) | 0.0058 (11) | −0.0002 (10) | −0.0035 (10) |
C32 | 0.047 (2) | 0.0441 (18) | 0.0268 (14) | 0.0088 (17) | 0.0006 (14) | −0.0095 (13) |
C33 | 0.0316 (17) | 0.0308 (14) | 0.0208 (13) | 0.0006 (12) | 0.0025 (11) | −0.0026 (11) |
C34 | 0.0381 (19) | 0.0408 (18) | 0.0381 (17) | −0.0102 (15) | 0.0085 (14) | −0.0060 (14) |
C35 | 0.0387 (19) | 0.0383 (17) | 0.0309 (15) | 0.0091 (15) | −0.0001 (13) | 0.0021 (13) |
N36 | 0.0264 (13) | 0.0330 (13) | 0.0200 (11) | −0.0001 (11) | 0.0034 (10) | 0.0003 (10) |
C41 | 0.0371 (18) | 0.0417 (18) | 0.0354 (16) | −0.0081 (15) | 0.0061 (15) | −0.0039 (14) |
C42 | 0.0363 (18) | 0.0447 (19) | 0.0366 (17) | −0.0149 (15) | 0.0003 (14) | 0.0086 (15) |
C43 | 0.050 (2) | 0.0312 (16) | 0.049 (2) | −0.0070 (16) | −0.0101 (17) | 0.0019 (15) |
C44 | 0.052 (2) | 0.0383 (19) | 0.076 (3) | −0.0032 (19) | 0.009 (2) | −0.0229 (18) |
C45 | 0.041 (2) | 0.0371 (17) | 0.061 (2) | −0.0005 (16) | 0.0085 (17) | −0.0091 (16) |
C46 | 0.0326 (18) | 0.0288 (13) | 0.0277 (13) | −0.0022 (12) | −0.0001 (12) | 0.0048 (11) |
C47 | 0.0282 (16) | 0.0361 (16) | 0.0393 (16) | −0.0051 (13) | 0.0070 (14) | −0.0060 (13) |
C48 | 0.0220 (13) | 0.0271 (13) | 0.0289 (13) | −0.0037 (12) | 0.0028 (12) | −0.0002 (11) |
C49 | 0.0245 (16) | 0.0347 (15) | 0.0267 (13) | −0.0009 (12) | 0.0012 (11) | 0.0005 (11) |
O50 | 0.0458 (14) | 0.0370 (11) | 0.0344 (11) | −0.0053 (11) | 0.0063 (11) | 0.0066 (9) |
N51 | 0.0334 (15) | 0.0341 (12) | 0.0244 (11) | −0.0047 (11) | 0.0033 (11) | 0.0016 (10) |
C52 | 0.055 (2) | 0.0471 (18) | 0.0257 (14) | −0.0105 (19) | 0.0005 (16) | −0.0022 (13) |
C53 | 0.0312 (16) | 0.0315 (14) | 0.0247 (13) | −0.0021 (12) | 0.0004 (11) | 0.0002 (11) |
C54 | 0.0373 (18) | 0.0317 (15) | 0.0360 (16) | −0.0089 (14) | −0.0040 (14) | 0.0042 (13) |
C55 | 0.0351 (19) | 0.0411 (17) | 0.0401 (17) | 0.0070 (15) | −0.0020 (14) | −0.0070 (14) |
N56 | 0.0263 (13) | 0.0301 (13) | 0.0240 (11) | −0.0019 (11) | 0.0007 (10) | −0.0004 (10) |
C1—C6 | 1.379 (5) | C29—O30 | 1.217 (3) |
C1—C2 | 1.403 (5) | C29—N31 | 1.343 (4) |
C1—H1 | 0.9500 | N31—C32 | 1.460 (4) |
C2—C3 | 1.381 (7) | N31—C33 | 1.472 (3) |
C2—H2 | 0.9500 | C32—H32A | 0.9800 |
C3—C4 | 1.367 (6) | C32—H32B | 0.9800 |
C3—H3 | 0.9500 | C32—H32C | 0.9800 |
C4—C5 | 1.389 (5) | C33—C35 | 1.511 (4) |
C4—H4 | 0.9500 | C33—C34 | 1.517 (4) |
C5—C6 | 1.393 (5) | C33—N36 | 1.526 (4) |
C5—H5 | 0.9500 | C34—H34A | 0.9800 |
C6—C7 | 1.510 (4) | C34—H34B | 0.9800 |
C7—C8 | 1.521 (4) | C34—H34C | 0.9800 |
C7—H7A | 0.9900 | C35—H35A | 0.9800 |
C7—H7B | 0.9900 | C35—H35B | 0.9800 |
C8—N16 | 1.488 (4) | C35—H35C | 0.9800 |
C8—C9 | 1.527 (4) | N36—H36A | 0.874 (17) |
C8—H8 | 1.0000 | N36—H36B | 0.884 (18) |
C9—O10 | 1.221 (3) | C41—C46 | 1.375 (4) |
C9—N11 | 1.330 (4) | C41—C42 | 1.390 (4) |
N11—C12 | 1.455 (4) | C41—H41 | 0.9500 |
N11—C13 | 1.465 (3) | C42—C43 | 1.363 (5) |
C12—H12A | 0.9800 | C42—H42 | 0.9500 |
C12—H12B | 0.9800 | C43—C44 | 1.371 (6) |
C12—H12C | 0.9800 | C43—H43 | 0.9500 |
C13—C15 | 1.506 (4) | C44—C45 | 1.379 (5) |
C13—N16 | 1.518 (4) | C44—H44 | 0.9500 |
C13—C14 | 1.522 (5) | C45—C46 | 1.384 (4) |
C14—H14A | 0.9800 | C45—H45 | 0.9500 |
C14—H14B | 0.9800 | C46—C47 | 1.518 (4) |
C14—H14C | 0.9800 | C47—C48 | 1.515 (4) |
C15—H15A | 0.9800 | C47—H47A | 0.9900 |
C15—H15B | 0.9800 | C47—H47B | 0.9900 |
C15—H15C | 0.9800 | C48—N56 | 1.490 (4) |
N16—H16A | 0.864 (18) | C48—C49 | 1.512 (4) |
N16—H16B | 0.867 (17) | C48—H48 | 1.0000 |
C21—C22 | 1.382 (5) | C49—O50 | 1.218 (3) |
C21—C26 | 1.387 (5) | C49—N51 | 1.350 (4) |
C21—H21 | 0.9500 | N51—C52 | 1.448 (4) |
C22—C23 | 1.367 (5) | N51—C53 | 1.473 (4) |
C22—H22 | 0.9500 | C52—H52A | 0.9800 |
C23—C24 | 1.379 (5) | C52—H52B | 0.9800 |
C23—H23 | 0.9500 | C52—H52C | 0.9800 |
C24—C25 | 1.390 (5) | C53—N56 | 1.508 (4) |
C24—H24 | 0.9500 | C53—C54 | 1.510 (4) |
C25—C26 | 1.377 (4) | C53—C55 | 1.514 (4) |
C25—H25 | 0.9500 | C54—H54A | 0.9800 |
C26—C27 | 1.502 (4) | C54—H54B | 0.9800 |
C27—C28 | 1.525 (4) | C54—H54C | 0.9800 |
C27—H27A | 0.9900 | C55—H55A | 0.9800 |
C27—H27B | 0.9900 | C55—H55B | 0.9800 |
C28—N36 | 1.500 (4) | C55—H55C | 0.9800 |
C28—C29 | 1.516 (4) | N56—H56A | 0.899 (17) |
C28—H28 | 1.0000 | N56—H56B | 0.869 (18) |
C6—C1—C2 | 119.8 (4) | C29—N31—C32 | 123.1 (2) |
C6—C1—H1 | 120.1 | C29—N31—C33 | 114.5 (2) |
C2—C1—H1 | 120.1 | C32—N31—C33 | 120.9 (2) |
C3—C2—C1 | 120.3 (4) | N31—C32—H32A | 109.5 |
C3—C2—H2 | 119.8 | N31—C32—H32B | 109.5 |
C1—C2—H2 | 119.8 | H32A—C32—H32B | 109.5 |
C4—C3—C2 | 119.9 (4) | N31—C32—H32C | 109.5 |
C4—C3—H3 | 120.0 | H32A—C32—H32C | 109.5 |
C2—C3—H3 | 120.0 | H32B—C32—H32C | 109.5 |
C3—C4—C5 | 120.3 (4) | N31—C33—C35 | 112.8 (2) |
C3—C4—H4 | 119.9 | N31—C33—C34 | 111.7 (3) |
C5—C4—H4 | 119.9 | C35—C33—C34 | 112.8 (3) |
C4—C5—C6 | 120.5 (4) | N31—C33—N36 | 99.4 (2) |
C4—C5—H5 | 119.7 | C35—C33—N36 | 109.5 (2) |
C6—C5—H5 | 119.7 | C34—C33—N36 | 109.8 (2) |
C1—C6—C5 | 119.2 (3) | C33—C34—H34A | 109.5 |
C1—C6—C7 | 118.6 (3) | C33—C34—H34B | 109.5 |
C5—C6—C7 | 121.8 (3) | H34A—C34—H34B | 109.5 |
C6—C7—C8 | 118.9 (3) | C33—C34—H34C | 109.5 |
C6—C7—H7A | 107.6 | H34A—C34—H34C | 109.5 |
C8—C7—H7A | 107.6 | H34B—C34—H34C | 109.5 |
C6—C7—H7B | 107.6 | C33—C35—H35A | 109.5 |
C8—C7—H7B | 107.6 | C33—C35—H35B | 109.5 |
H7A—C7—H7B | 107.0 | H35A—C35—H35B | 109.5 |
N16—C8—C7 | 115.4 (3) | C33—C35—H35C | 109.5 |
N16—C8—C9 | 101.8 (2) | H35A—C35—H35C | 109.5 |
C7—C8—C9 | 109.7 (2) | H35B—C35—H35C | 109.5 |
N16—C8—H8 | 109.9 | C28—N36—C33 | 107.2 (2) |
C7—C8—H8 | 109.9 | C28—N36—H36A | 111 (2) |
C9—C8—H8 | 109.9 | C33—N36—H36A | 117 (2) |
O10—C9—N11 | 127.2 (3) | C28—N36—H36B | 107 (2) |
O10—C9—C8 | 124.4 (3) | C33—N36—H36B | 108 (2) |
N11—C9—C8 | 108.5 (2) | H36A—N36—H36B | 106 (3) |
C9—N11—C12 | 122.1 (2) | C46—C41—C42 | 120.9 (3) |
C9—N11—C13 | 114.4 (2) | C46—C41—H41 | 119.5 |
C12—N11—C13 | 121.7 (2) | C42—C41—H41 | 119.5 |
N11—C12—H12A | 109.5 | C43—C42—C41 | 120.7 (3) |
N11—C12—H12B | 109.5 | C43—C42—H42 | 119.7 |
H12A—C12—H12B | 109.5 | C41—C42—H42 | 119.7 |
N11—C12—H12C | 109.5 | C42—C43—C44 | 119.1 (3) |
H12A—C12—H12C | 109.5 | C42—C43—H43 | 120.4 |
H12B—C12—H12C | 109.5 | C44—C43—H43 | 120.4 |
N11—C13—C15 | 112.6 (2) | C43—C44—C45 | 120.3 (4) |
N11—C13—N16 | 99.6 (2) | C43—C44—H44 | 119.9 |
C15—C13—N16 | 109.2 (3) | C45—C44—H44 | 119.9 |
N11—C13—C14 | 111.0 (3) | C44—C45—C46 | 121.4 (4) |
C15—C13—C14 | 113.2 (3) | C44—C45—H45 | 119.3 |
N16—C13—C14 | 110.5 (3) | C46—C45—H45 | 119.3 |
C13—C14—H14A | 109.5 | C41—C46—C45 | 117.6 (3) |
C13—C14—H14B | 109.5 | C41—C46—C47 | 124.1 (3) |
H14A—C14—H14B | 109.5 | C45—C46—C47 | 118.2 (3) |
C13—C14—H14C | 109.5 | C48—C47—C46 | 116.2 (3) |
H14A—C14—H14C | 109.5 | C48—C47—H47A | 108.2 |
H14B—C14—H14C | 109.5 | C46—C47—H47A | 108.2 |
C13—C15—H15A | 109.5 | C48—C47—H47B | 108.2 |
C13—C15—H15B | 109.5 | C46—C47—H47B | 108.2 |
H15A—C15—H15B | 109.5 | H47A—C47—H47B | 107.4 |
C13—C15—H15C | 109.5 | N56—C48—C49 | 101.8 (2) |
H15A—C15—H15C | 109.5 | N56—C48—C47 | 112.0 (2) |
H15B—C15—H15C | 109.5 | C49—C48—C47 | 115.6 (3) |
C8—N16—C13 | 107.6 (2) | N56—C48—H48 | 109.1 |
C8—N16—H16A | 110 (2) | C49—C48—H48 | 109.1 |
C13—N16—H16A | 106 (2) | C47—C48—H48 | 109.1 |
C8—N16—H16B | 120 (2) | O50—C49—N51 | 126.3 (3) |
C13—N16—H16B | 110 (2) | O50—C49—C48 | 125.5 (3) |
H16A—N16—H16B | 101 (3) | N51—C49—C48 | 108.2 (2) |
C22—C21—C26 | 120.7 (3) | C49—N51—C52 | 123.1 (3) |
C22—C21—H21 | 119.7 | C49—N51—C53 | 114.4 (2) |
C26—C21—H21 | 119.7 | C52—N51—C53 | 121.8 (2) |
C23—C22—C21 | 120.2 (4) | N51—C52—H52A | 109.5 |
C23—C22—H22 | 119.9 | N51—C52—H52B | 109.5 |
C21—C22—H22 | 119.9 | H52A—C52—H52B | 109.5 |
C22—C23—C24 | 120.0 (3) | N51—C52—H52C | 109.5 |
C22—C23—H23 | 120.0 | H52A—C52—H52C | 109.5 |
C24—C23—H23 | 120.0 | H52B—C52—H52C | 109.5 |
C23—C24—C25 | 119.7 (3) | N51—C53—N56 | 99.5 (2) |
C23—C24—H24 | 120.1 | N51—C53—C54 | 112.9 (2) |
C25—C24—H24 | 120.1 | N56—C53—C54 | 109.9 (2) |
C26—C25—C24 | 120.8 (4) | N51—C53—C55 | 111.7 (3) |
C26—C25—H25 | 119.6 | N56—C53—C55 | 109.9 (2) |
C24—C25—H25 | 119.6 | C54—C53—C55 | 112.3 (3) |
C25—C26—C21 | 118.5 (3) | C53—C54—H54A | 109.5 |
C25—C26—C27 | 120.7 (3) | C53—C54—H54B | 109.5 |
C21—C26—C27 | 120.8 (3) | H54A—C54—H54B | 109.5 |
C26—C27—C28 | 114.3 (2) | C53—C54—H54C | 109.5 |
C26—C27—H27A | 108.7 | H54A—C54—H54C | 109.5 |
C28—C27—H27A | 108.7 | H54B—C54—H54C | 109.5 |
C26—C27—H27B | 108.7 | C53—C55—H55A | 109.5 |
C28—C27—H27B | 108.7 | C53—C55—H55B | 109.5 |
H27A—C27—H27B | 107.6 | H55A—C55—H55B | 109.5 |
N36—C28—C29 | 101.4 (2) | C53—C55—H55C | 109.5 |
N36—C28—C27 | 114.5 (2) | H55A—C55—H55C | 109.5 |
C29—C28—C27 | 114.0 (2) | H55B—C55—H55C | 109.5 |
N36—C28—H28 | 108.9 | C48—N56—C53 | 108.5 (2) |
C29—C28—H28 | 108.9 | C48—N56—H56A | 110 (2) |
C27—C28—H28 | 108.9 | C53—N56—H56A | 117 (2) |
O30—C29—N31 | 126.5 (3) | C48—N56—H56B | 104 (2) |
O30—C29—C28 | 125.0 (3) | C53—N56—H56B | 110 (2) |
N31—C29—C28 | 108.5 (2) | H56A—N56—H56B | 107 (3) |
C13H19N2O+·Cl−·H2O | F(000) = 292 |
Mr = 272.77 | Dx = 1.251 Mg m−3 |
Monoclinic, P21 | Synchrotron radiation, λ = 0.79770 Å |
Hall symbol: P 2yb | Cell parameters from 1277 reflections |
a = 9.6320 (19) Å | θ = 3.7–25.6° |
b = 7.0446 (14) Å | µ = 0.26 mm−1 |
c = 11.093 (2) Å | T = 150 K |
β = 105.82 (3)° | Block, colourless |
V = 724.2 (3) Å3 | 0.08 × 0.03 × 0.01 mm |
Z = 2 |
Bruker D8 diffractometer | 3480 independent reflections |
Radiation source: Daresbury SRS, Station 16.2SMX | 2485 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.049 |
ω rotation with narrow frame scans | θmax = 32.1°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −12→12 |
Tmin = 0.979, Tmax = 1 | k = −9→9 |
6282 measured reflections | l = −13→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0587P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
3480 reflections | Δρmax = 0.30 e Å−3 |
182 parameters | Δρmin = −0.39 e Å−3 |
5 restraints | Absolute structure: Flack (1983), 1545 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.15 (9) |
C13H19N2O+·Cl−·H2O | V = 724.2 (3) Å3 |
Mr = 272.77 | Z = 2 |
Monoclinic, P21 | Synchrotron radiation, λ = 0.79770 Å |
a = 9.6320 (19) Å | µ = 0.26 mm−1 |
b = 7.0446 (14) Å | T = 150 K |
c = 11.093 (2) Å | 0.08 × 0.03 × 0.01 mm |
β = 105.82 (3)° |
Bruker D8 diffractometer | 3480 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2485 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 1 | Rint = 0.049 |
6282 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | Δρmax = 0.30 e Å−3 |
S = 0.96 | Δρmin = −0.39 e Å−3 |
3480 reflections | Absolute structure: Flack (1983), 1545 Friedel pairs |
182 parameters | Absolute structure parameter: −0.15 (9) |
5 restraints |
Experimental. A correction to account for beam decay and for absorption was applied using SADABS. Ratio of min/max transmission 0.450. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1W | 0.5949 (3) | 0.5880 (4) | 0.5927 (2) | 0.0357 (6) | |
Cl1 | 0.73236 (8) | −0.01536 (10) | 0.53347 (8) | 0.0319 (2) | |
C1 | 0.6492 (3) | 0.0160 (4) | 0.9371 (3) | 0.0275 (8) | |
H1 | 0.7328 | 0.0349 | 1.0049 | 0.033* | |
C2 | 0.5814 (4) | −0.1589 (5) | 0.9230 (3) | 0.0316 (8) | |
H2 | 0.6168 | −0.2581 | 0.9813 | 0.038* | |
C3 | 0.4610 (4) | −0.1874 (5) | 0.8225 (4) | 0.0366 (9) | |
H3 | 0.4141 | −0.3073 | 0.8111 | 0.044* | |
C4 | 0.4093 (4) | −0.0425 (6) | 0.7392 (4) | 0.0420 (10) | |
H4 | 0.3270 | −0.0633 | 0.6705 | 0.050* | |
C5 | 0.4760 (4) | 0.1329 (5) | 0.7547 (3) | 0.0337 (8) | |
H5 | 0.4387 | 0.2323 | 0.6970 | 0.040* | |
C6 | 0.5980 (3) | 0.1646 (4) | 0.8548 (3) | 0.0229 (7) | |
C7 | 0.6727 (3) | 0.3548 (5) | 0.8741 (3) | 0.0248 (7) | |
H7A | 0.6875 | 0.3946 | 0.9622 | 0.030* | |
H7B | 0.6097 | 0.4500 | 0.8199 | 0.030* | |
C8 | 0.8174 (3) | 0.3514 (4) | 0.8443 (3) | 0.0221 (7) | |
H8 | 0.8758 | 0.2427 | 0.8894 | 0.027* | |
C9 | 0.9036 (3) | 0.5347 (4) | 0.8786 (3) | 0.0222 (7) | |
O10 | 0.9149 (2) | 0.6252 (3) | 0.9741 (2) | 0.0328 (6) | |
N11 | 0.9619 (3) | 0.5769 (4) | 0.7829 (2) | 0.0222 (6) | |
C12 | 1.0484 (4) | 0.7448 (5) | 0.7802 (4) | 0.0319 (8) | |
H12A | 1.0464 | 0.8278 | 0.8506 | 0.048* | |
H12B | 1.0092 | 0.8129 | 0.7012 | 0.048* | |
H12C | 1.1482 | 0.7069 | 0.7870 | 0.048* | |
C13 | 0.9429 (3) | 0.4239 (4) | 0.6898 (3) | 0.0207 (7) | |
C14 | 1.0675 (4) | 0.2802 (5) | 0.7256 (3) | 0.0286 (8) | |
H14A | 1.1573 | 0.3418 | 0.7213 | 0.043* | |
H14B | 1.0468 | 0.1728 | 0.6673 | 0.043* | |
H14C | 1.0780 | 0.2344 | 0.8111 | 0.043* | |
C15 | 0.9194 (3) | 0.4956 (5) | 0.5573 (3) | 0.0264 (7) | |
H15A | 0.8461 | 0.5958 | 0.5406 | 0.040* | |
H15B | 0.8868 | 0.3908 | 0.4983 | 0.040* | |
H15C | 1.0102 | 0.5466 | 0.5471 | 0.040* | |
N16 | 0.8062 (3) | 0.3367 (4) | 0.7071 (2) | 0.0217 (6) | |
H1B | 0.500 (3) | 0.554 (7) | 0.555 (4) | 0.091 (19)* | |
H1A | 0.617 (5) | 0.711 (4) | 0.578 (5) | 0.085 (18)* | |
H16B | 0.729 (3) | 0.400 (4) | 0.667 (3) | 0.021 (9)* | |
H16A | 0.795 (4) | 0.229 (4) | 0.666 (3) | 0.041 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.0283 (14) | 0.0269 (14) | 0.0457 (16) | 0.0008 (11) | 0.0000 (12) | 0.0063 (11) |
Cl1 | 0.0281 (4) | 0.0207 (4) | 0.0442 (5) | −0.0007 (4) | 0.0055 (3) | −0.0096 (4) |
C1 | 0.0294 (17) | 0.022 (2) | 0.0291 (17) | −0.0003 (14) | 0.0048 (14) | 0.0016 (14) |
C2 | 0.0321 (19) | 0.0202 (17) | 0.042 (2) | 0.0029 (15) | 0.0095 (16) | 0.0036 (16) |
C3 | 0.032 (2) | 0.026 (2) | 0.055 (3) | −0.0051 (15) | 0.0166 (19) | −0.0030 (17) |
C4 | 0.0298 (19) | 0.041 (3) | 0.046 (2) | −0.0100 (18) | −0.0045 (17) | −0.0030 (19) |
C5 | 0.0286 (19) | 0.0303 (19) | 0.038 (2) | −0.0013 (15) | 0.0020 (16) | 0.0058 (16) |
C6 | 0.0236 (17) | 0.0196 (16) | 0.0265 (17) | −0.0011 (13) | 0.0084 (14) | −0.0012 (13) |
C7 | 0.0270 (17) | 0.0197 (16) | 0.0289 (17) | 0.0014 (13) | 0.0093 (14) | 0.0010 (14) |
C8 | 0.0258 (17) | 0.0150 (14) | 0.0257 (17) | 0.0025 (13) | 0.0074 (14) | 0.0035 (13) |
C9 | 0.0221 (16) | 0.0168 (16) | 0.0254 (16) | 0.0023 (11) | 0.0027 (13) | 0.0011 (12) |
O10 | 0.0336 (14) | 0.0347 (14) | 0.0283 (13) | −0.0061 (11) | 0.0055 (11) | −0.0105 (11) |
N11 | 0.0259 (14) | 0.0141 (12) | 0.0242 (14) | −0.0034 (11) | 0.0029 (11) | 0.0004 (10) |
C12 | 0.031 (2) | 0.0214 (17) | 0.042 (2) | −0.0088 (14) | 0.0071 (17) | 0.0043 (15) |
C13 | 0.0216 (16) | 0.0161 (15) | 0.0239 (17) | −0.0007 (11) | 0.0051 (13) | 0.0002 (12) |
C14 | 0.0279 (18) | 0.0227 (17) | 0.036 (2) | 0.0042 (14) | 0.0101 (16) | 0.0061 (14) |
C15 | 0.0307 (16) | 0.0235 (16) | 0.0255 (16) | 0.0023 (17) | 0.0083 (13) | 0.0038 (15) |
N16 | 0.0228 (14) | 0.0180 (13) | 0.0228 (15) | −0.0017 (11) | 0.0040 (12) | −0.0033 (11) |
O1W—H1B | 0.93 (2) | C8—H8 | 1.0000 |
O1W—H1A | 0.92 (2) | C9—O10 | 1.215 (4) |
C1—C2 | 1.383 (5) | C9—N11 | 1.362 (4) |
C1—C6 | 1.388 (4) | N11—C12 | 1.452 (4) |
C1—H1 | 0.9500 | N11—C13 | 1.470 (4) |
C2—C3 | 1.387 (5) | C12—H12A | 0.9800 |
C2—H2 | 0.9500 | C12—H12B | 0.9800 |
C3—C4 | 1.375 (5) | C12—H12C | 0.9800 |
C3—H3 | 0.9500 | C13—C15 | 1.512 (4) |
C4—C5 | 1.382 (5) | C13—N16 | 1.512 (4) |
C4—H4 | 0.9500 | C13—C14 | 1.538 (4) |
C5—C6 | 1.398 (5) | C14—H14A | 0.9800 |
C5—H5 | 0.9500 | C14—H14B | 0.9800 |
C6—C7 | 1.508 (5) | C14—H14C | 0.9800 |
C7—C8 | 1.517 (4) | C15—H15A | 0.9800 |
C7—H7A | 0.9900 | C15—H15B | 0.9800 |
C7—H7B | 0.9900 | C15—H15C | 0.9800 |
C8—N16 | 1.500 (4) | N16—H16B | 0.877 (18) |
C8—C9 | 1.526 (4) | N16—H16A | 0.877 (19) |
H1B—O1W—H1A | 114 (5) | C9—N11—C12 | 123.7 (3) |
C2—C1—C6 | 121.7 (3) | C9—N11—C13 | 112.9 (2) |
C2—C1—H1 | 119.1 | C12—N11—C13 | 123.0 (3) |
C6—C1—H1 | 119.1 | N11—C12—H12A | 109.5 |
C1—C2—C3 | 119.0 (3) | N11—C12—H12B | 109.5 |
C1—C2—H2 | 120.5 | H12A—C12—H12B | 109.5 |
C3—C2—H2 | 120.5 | N11—C12—H12C | 109.5 |
C4—C3—C2 | 120.2 (3) | H12A—C12—H12C | 109.5 |
C4—C3—H3 | 119.9 | H12B—C12—H12C | 109.5 |
C2—C3—H3 | 119.9 | N11—C13—C15 | 113.3 (2) |
C3—C4—C5 | 120.6 (3) | N11—C13—N16 | 98.9 (2) |
C3—C4—H4 | 119.7 | C15—C13—N16 | 110.8 (2) |
C5—C4—H4 | 119.7 | N11—C13—C14 | 111.2 (3) |
C4—C5—C6 | 120.2 (3) | C15—C13—C14 | 111.7 (3) |
C4—C5—H5 | 119.9 | N16—C13—C14 | 110.2 (3) |
C6—C5—H5 | 119.9 | C13—C14—H14A | 109.5 |
C1—C6—C5 | 118.2 (3) | C13—C14—H14B | 109.5 |
C1—C6—C7 | 120.5 (3) | H14A—C14—H14B | 109.5 |
C5—C6—C7 | 121.3 (3) | C13—C14—H14C | 109.5 |
C6—C7—C8 | 112.7 (3) | H14A—C14—H14C | 109.5 |
C6—C7—H7A | 109.0 | H14B—C14—H14C | 109.5 |
C8—C7—H7A | 109.0 | C13—C15—H15A | 109.5 |
C6—C7—H7B | 109.0 | C13—C15—H15B | 109.5 |
C8—C7—H7B | 109.0 | H15A—C15—H15B | 109.5 |
H7A—C7—H7B | 107.8 | C13—C15—H15C | 109.5 |
N16—C8—C7 | 113.9 (3) | H15A—C15—H15C | 109.5 |
N16—C8—C9 | 101.3 (2) | H15B—C15—H15C | 109.5 |
C7—C8—C9 | 113.7 (3) | C8—N16—C13 | 106.1 (2) |
N16—C8—H8 | 109.2 | C8—N16—H16B | 108 (2) |
C7—C8—H8 | 109.2 | C13—N16—H16B | 112 (2) |
C9—C8—H8 | 109.2 | C8—N16—H16A | 123 (3) |
O10—C9—N11 | 127.3 (3) | C13—N16—H16A | 106 (2) |
O10—C9—C8 | 125.1 (3) | H16B—N16—H16A | 102 (3) |
N11—C9—C8 | 107.6 (3) |
C13H19N2O+·Cl−·H2O | F(000) = 292 |
Mr = 272.77 | Dx = 1.249 Mg m−3 |
Monoclinic, P21 | Synchrotron radiation, λ = 0.79770 Å |
Hall symbol: P 2yb | Cell parameters from 914 reflections |
a = 9.6425 (14) Å | θ = 3.7–24.1° |
b = 7.0517 (10) Å | µ = 0.26 mm−1 |
c = 11.0895 (16) Å | T = 150 K |
β = 105.796 (2)° | Square plate, colourless |
V = 725.57 (18) Å3 | 0.04 × 0.04 × 0.01 mm |
Z = 2 |
Bruker D8 diffractometer | 3330 independent reflections |
Radiation source: Daresbury SRS, Station 16.2SMX | 2438 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.052 |
ω rotation with narrow frame scans | θmax = 32.4°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −12→12 |
Tmin = 0.987, Tmax = 0.99 | k = −9→9 |
6377 measured reflections | l = −14→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0529P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
3330 reflections | Δρmax = 0.27 e Å−3 |
181 parameters | Δρmin = −0.38 e Å−3 |
5 restraints | Absolute structure: Flack (1983), 1339 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (9) |
C13H19N2O+·Cl−·H2O | V = 725.57 (18) Å3 |
Mr = 272.77 | Z = 2 |
Monoclinic, P21 | Synchrotron radiation, λ = 0.79770 Å |
a = 9.6425 (14) Å | µ = 0.26 mm−1 |
b = 7.0517 (10) Å | T = 150 K |
c = 11.0895 (16) Å | 0.04 × 0.04 × 0.01 mm |
β = 105.796 (2)° |
Bruker D8 diffractometer | 3330 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2438 reflections with I > 2σ(I) |
Tmin = 0.987, Tmax = 0.99 | Rint = 0.052 |
6377 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | Δρmax = 0.27 e Å−3 |
S = 0.98 | Δρmin = −0.38 e Å−3 |
3330 reflections | Absolute structure: Flack (1983), 1339 Friedel pairs |
181 parameters | Absolute structure parameter: −0.01 (9) |
5 restraints |
Experimental. A correction to account for beam decay and for absorption was applied using SADABS. Ratio of min/max transmission 0.56. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1W | 0.4053 (3) | 0.4119 (4) | 0.4073 (3) | 0.0331 (6) | |
H1B | 0.499 (3) | 0.441 (7) | 0.453 (4) | 0.089 (14)* | |
H1A | 0.386 (6) | 0.289 (4) | 0.423 (5) | 0.089 (14)* | |
Cl1 | 0.26752 (8) | 1.01537 (11) | 0.46663 (8) | 0.0286 (2) | |
C1 | 0.3516 (4) | 0.9829 (5) | 0.0632 (3) | 0.0251 (8) | |
H1 | 0.2683 | 0.9634 | −0.0048 | 0.030* | |
C2 | 0.4190 (4) | 1.1592 (5) | 0.0771 (3) | 0.0294 (8) | |
H2 | 0.3828 | 1.2587 | 0.0193 | 0.035* | |
C3 | 0.5404 (4) | 1.1868 (6) | 0.1773 (4) | 0.0347 (9) | |
H3 | 0.5883 | 1.3058 | 0.1880 | 0.042* | |
C4 | 0.5914 (4) | 1.0420 (6) | 0.2610 (4) | 0.0388 (10) | |
H4 | 0.6730 | 1.0627 | 0.3303 | 0.047* | |
C5 | 0.5247 (4) | 0.8670 (5) | 0.2448 (3) | 0.0292 (8) | |
H5 | 0.5626 | 0.7673 | 0.3020 | 0.035* | |
C6 | 0.4024 (4) | 0.8347 (5) | 0.1457 (3) | 0.0199 (7) | |
C7 | 0.3281 (3) | 0.6452 (5) | 0.1261 (3) | 0.0216 (7) | |
H7A | 0.3906 | 0.5500 | 0.1806 | 0.026* | |
H7B | 0.3141 | 0.6053 | 0.0380 | 0.026* | |
C8 | 0.1818 (3) | 0.6490 (5) | 0.1551 (3) | 0.0178 (7) | |
H8 | 0.1231 | 0.7572 | 0.1098 | 0.021* | |
C9 | 0.0976 (3) | 0.4657 (4) | 0.1218 (3) | 0.0186 (7) | |
O10 | 0.0850 (2) | 0.3747 (4) | 0.0258 (2) | 0.0288 (6) | |
N11 | 0.0383 (3) | 0.4234 (4) | 0.2169 (2) | 0.0195 (6) | |
C12 | −0.0486 (4) | 0.2561 (5) | 0.2200 (3) | 0.0284 (8) | |
H12A | −0.0527 | 0.1774 | 0.1462 | 0.043* | |
H12B | −0.1463 | 0.2949 | 0.2195 | 0.043* | |
H12C | −0.0053 | 0.1832 | 0.2962 | 0.043* | |
C13 | 0.0567 (3) | 0.5769 (4) | 0.3105 (3) | 0.0180 (7) | |
C14 | −0.0673 (4) | 0.7197 (5) | 0.2744 (3) | 0.0235 (7) | |
H14A | −0.1569 | 0.6584 | 0.2791 | 0.035* | |
H14B | −0.0778 | 0.7646 | 0.1888 | 0.035* | |
H14C | −0.0465 | 0.8275 | 0.3323 | 0.035* | |
C15 | 0.0808 (3) | 0.5036 (6) | 0.4428 (3) | 0.0241 (7) | |
H15A | 0.1505 | 0.3992 | 0.4573 | 0.036* | |
H15B | −0.0107 | 0.4579 | 0.4543 | 0.036* | |
H15C | 0.1182 | 0.6061 | 0.5024 | 0.036* | |
N16 | 0.1943 (3) | 0.6638 (4) | 0.2933 (2) | 0.0179 (6) | |
H16B | 0.265 (3) | 0.585 (5) | 0.330 (4) | 0.056 (14)* | |
H16A | 0.206 (4) | 0.777 (3) | 0.327 (4) | 0.046 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.0236 (13) | 0.0284 (15) | 0.0403 (16) | 0.0039 (12) | −0.0032 (11) | 0.0087 (12) |
Cl1 | 0.0241 (4) | 0.0222 (4) | 0.0367 (5) | −0.0002 (4) | 0.0034 (3) | −0.0085 (4) |
C1 | 0.0295 (17) | 0.023 (2) | 0.0203 (17) | −0.0003 (15) | 0.0031 (13) | 0.0020 (14) |
C2 | 0.032 (2) | 0.0206 (18) | 0.037 (2) | −0.0014 (16) | 0.0108 (17) | 0.0004 (16) |
C3 | 0.029 (2) | 0.030 (2) | 0.048 (2) | −0.0045 (17) | 0.0160 (19) | −0.0012 (19) |
C4 | 0.0258 (19) | 0.042 (3) | 0.040 (2) | −0.0091 (19) | −0.0063 (16) | 0.002 (2) |
C5 | 0.0249 (19) | 0.032 (2) | 0.0273 (19) | 0.0010 (16) | 0.0004 (15) | 0.0080 (16) |
C6 | 0.0211 (17) | 0.0214 (17) | 0.0177 (16) | 0.0041 (14) | 0.0061 (13) | 0.0014 (13) |
C7 | 0.0215 (17) | 0.0229 (18) | 0.0205 (16) | 0.0001 (14) | 0.0060 (13) | 0.0015 (14) |
C8 | 0.0212 (16) | 0.0179 (16) | 0.0143 (15) | −0.0046 (14) | 0.0047 (12) | −0.0005 (13) |
C9 | 0.0186 (16) | 0.0158 (17) | 0.0189 (16) | 0.0002 (12) | 0.0009 (13) | 0.0005 (12) |
O10 | 0.0314 (14) | 0.0339 (14) | 0.0191 (12) | −0.0060 (12) | 0.0033 (10) | −0.0078 (11) |
N11 | 0.0212 (14) | 0.0174 (13) | 0.0187 (14) | −0.0060 (12) | 0.0035 (11) | −0.0006 (11) |
C12 | 0.029 (2) | 0.0274 (19) | 0.027 (2) | −0.0064 (16) | 0.0051 (16) | 0.0018 (15) |
C13 | 0.0164 (16) | 0.0158 (15) | 0.0207 (17) | 0.0013 (12) | 0.0034 (13) | 0.0010 (12) |
C14 | 0.0229 (18) | 0.0238 (18) | 0.0228 (18) | 0.0050 (15) | 0.0044 (14) | 0.0017 (14) |
C15 | 0.0269 (16) | 0.0253 (17) | 0.0196 (16) | −0.0021 (19) | 0.0057 (12) | 0.0011 (16) |
N16 | 0.0197 (14) | 0.0148 (14) | 0.0173 (14) | 0.0007 (12) | 0.0021 (11) | −0.0019 (12) |
O1W—H1B | 0.93 (2) | C8—H8 | 1.0000 |
O1W—H1A | 0.912 (19) | C9—O10 | 1.220 (4) |
C1—C6 | 1.388 (4) | C9—N11 | 1.362 (4) |
C1—C2 | 1.392 (5) | N11—C12 | 1.453 (4) |
C1—H1 | 0.9500 | N11—C13 | 1.476 (4) |
C2—C3 | 1.391 (5) | C12—H12A | 0.9800 |
C2—H2 | 0.9500 | C12—H12B | 0.9800 |
C3—C4 | 1.377 (6) | C12—H12C | 0.9800 |
C3—H3 | 0.9500 | C13—C15 | 1.512 (4) |
C4—C5 | 1.381 (5) | C13—N16 | 1.520 (4) |
C4—H4 | 0.9500 | C13—C14 | 1.531 (4) |
C5—C6 | 1.395 (5) | C14—H14A | 0.9800 |
C5—H5 | 0.9500 | C14—H14B | 0.9800 |
C6—C7 | 1.504 (5) | C14—H14C | 0.9800 |
C7—C8 | 1.530 (4) | C15—H15A | 0.9800 |
C7—H7A | 0.9900 | C15—H15B | 0.9800 |
C7—H7B | 0.9900 | C15—H15C | 0.9800 |
C8—N16 | 1.508 (4) | N16—H16B | 0.89 (2) |
C8—C9 | 1.517 (4) | N16—H16A | 0.874 (19) |
H1B—O1W—H1A | 109 (5) | C9—N11—C12 | 124.2 (3) |
C6—C1—C2 | 122.0 (3) | C9—N11—C13 | 112.9 (2) |
C6—C1—H1 | 119.0 | C12—N11—C13 | 122.6 (3) |
C2—C1—H1 | 119.0 | N11—C12—H12A | 109.5 |
C3—C2—C1 | 118.6 (3) | N11—C12—H12B | 109.5 |
C3—C2—H2 | 120.7 | H12A—C12—H12B | 109.5 |
C1—C2—H2 | 120.7 | N11—C12—H12C | 109.5 |
C4—C3—C2 | 120.2 (4) | H12A—C12—H12C | 109.5 |
C4—C3—H3 | 119.9 | H12B—C12—H12C | 109.5 |
C2—C3—H3 | 119.9 | N11—C13—C15 | 112.9 (3) |
C3—C4—C5 | 120.5 (3) | N11—C13—N16 | 98.6 (2) |
C3—C4—H4 | 119.8 | C15—C13—N16 | 110.6 (2) |
C5—C4—H4 | 119.8 | N11—C13—C14 | 111.2 (3) |
C4—C5—C6 | 120.8 (3) | C15—C13—C14 | 112.4 (3) |
C4—C5—H5 | 119.6 | N16—C13—C14 | 110.4 (3) |
C6—C5—H5 | 119.6 | C13—C14—H14A | 109.5 |
C1—C6—C5 | 117.9 (3) | C13—C14—H14B | 109.5 |
C1—C6—C7 | 120.4 (3) | H14A—C14—H14B | 109.5 |
C5—C6—C7 | 121.8 (3) | C13—C14—H14C | 109.5 |
C6—C7—C8 | 112.6 (3) | H14A—C14—H14C | 109.5 |
C6—C7—H7A | 109.1 | H14B—C14—H14C | 109.5 |
C8—C7—H7A | 109.1 | C13—C15—H15A | 109.5 |
C6—C7—H7B | 109.1 | C13—C15—H15B | 109.5 |
C8—C7—H7B | 109.1 | H15A—C15—H15B | 109.5 |
H7A—C7—H7B | 107.8 | C13—C15—H15C | 109.5 |
N16—C8—C9 | 101.3 (2) | H15A—C15—H15C | 109.5 |
N16—C8—C7 | 113.1 (2) | H15B—C15—H15C | 109.5 |
C9—C8—C7 | 113.4 (3) | C8—N16—C13 | 105.6 (2) |
N16—C8—H8 | 109.6 | C8—N16—H16B | 106 (3) |
C9—C8—H8 | 109.6 | C13—N16—H16B | 106 (3) |
C7—C8—H8 | 109.6 | C8—N16—H16A | 117 (3) |
O10—C9—N11 | 126.7 (3) | C13—N16—H16A | 109 (3) |
O10—C9—C8 | 125.4 (3) | H16B—N16—H16A | 112 (4) |
N11—C9—C8 | 107.9 (3) |
Experimental details
(S2.HCl) | (R3) | (S3) | (R4) | |
Crystal data | ||||
Chemical formula | C10H15N2O+·Cl− | C13H19N2O+·Cl− | C13H19N2O+·Cl− | C13H19N2O+·Cl−·H2O |
Mr | 214.69 | 254.75 | 254.75 | 272.77 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 150 | 150 | 150 | 150 |
a, b, c (Å) | 4.9758 (7), 8.6213 (13), 25.521 (4) | 7.1167 (14), 19.237 (4), 30.370 (6) | 7.123 (1), 19.232 (3), 30.384 (4) | 9.6320 (19), 7.0446 (14), 11.093 (2) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 | 90, 105.82 (3), 90 |
V (Å3) | 1094.8 (3) | 4157.7 (14) | 4162.3 (10) | 724.2 (3) |
Z | 4 | 12 | 12 | 2 |
Radiation type | Synchrotron, λ = 0.69040 Å | Synchrotron, λ = 0.69040 Å | Synchrotron, λ = 0.69040 Å | Synchrotron, λ = 0.79770 Å |
µ (mm−1) | 0.32 | 0.26 | 0.26 | 0.26 |
Crystal size (mm) | 0.15 × 0.07 × 0.07 | 0.1 × 0.08 × 0.04 | 0.2 × 0.06 × 0.04 | 0.08 × 0.03 × 0.01 |
Data collection | ||||
Diffractometer | Bruker D8 diffractometer | Bruker D8 diffractometer | Bruker D8 diffractometer | Bruker D8 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.953, 0.978 | 0.974, 0.990 | 0.949, 0.990 | 0.979, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12758, 3619, 2971 | 24370, 9772, 7354 | 48955, 13171, 8896 | 6282, 3480, 2485 |
Rint | 0.091 | 0.071 | 0.126 | 0.049 |
(sin θ/λ)max (Å−1) | 0.750 | 0.662 | 0.724 | 0.667 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.157, 1.00 | 0.056, 0.131, 0.99 | 0.071, 0.171, 1.03 | 0.056, 0.130, 0.96 |
No. of reflections | 3619 | 9772 | 13171 | 3480 |
No. of parameters | 141 | 488 | 488 | 182 |
No. of restraints | 4 | 6 | 6 | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.58, −0.57 | 0.28, −0.23 | 0.46, −0.32 | 0.30, −0.39 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack (1983), 1545 Friedel pairs |
Absolute structure parameter | −0.01 (9) | 0.00 (6) | 0.09 (6) | −0.15 (9) |
(S4) | |
Crystal data | |
Chemical formula | C13H19N2O+·Cl−·H2O |
Mr | 272.77 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 150 |
a, b, c (Å) | 9.6425 (14), 7.0517 (10), 11.0895 (16) |
α, β, γ (°) | 90, 105.796 (2), 90 |
V (Å3) | 725.57 (18) |
Z | 2 |
Radiation type | Synchrotron, λ = 0.79770 Å |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.04 × 0.04 × 0.01 |
Data collection | |
Diffractometer | Bruker D8 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.987, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6377, 3330, 2438 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.122, 0.98 |
No. of reflections | 3330 |
No. of parameters | 181 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.38 |
Absolute structure | Flack (1983), 1339 Friedel pairs |
Absolute structure parameter | −0.01 (9) |
Computer programs: APEX2 (Bruker, 2004), APEXII (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Version 1.64; Farrugia, 1999).
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A number of research groups have reported on the utility of chiral imidazolidinone catalysts for a range of enantioselective organic reactions (Ahrendt et al., 2000; Wilson et al., 2005; Paras & MacMillan, 2001; Jen et al., 2000; Marigo et al., 2005; Kunz & MacMillan, 2005; Beeson & MacMillan, 2005; Brochu et al., 2004). Several reviews of the field of organocatalysis exist (Almaşi et al., 2007; Bolm et al., 2005; Gaunt et al., 2007; Tsogoeva 2007; List 2006). Enantiomeric excesses greater than 90% are regularly achieved in relatively high yielding reactions that are difficult to accomplish by other means. However, there are to date very few structural studies of these materials, and no reports of their stability to storage or recrystallization. Both of these factors are expected to be highly relevant to possible use of the materials in both industrial and laboratory settings.
The catalyst studied in the current work is a typical example of the class (Ahrendt et al., 2000), is commercially available, and has been described as `an inexpensive, bench-stable solid that is readily handled by experimentalists or automated systems' (Beeson & MacMillan, 2005). We therefore selected this compound for a full structural characterization, which is of interest both to confirm the reported molecular structure of this material, and with a view to rationalizing its solid-state properties, including particle morphology and flow, solubility, stability etc. Synchrotron radiation was employed in order to gain the best quality structural information from these weakly scattering materials and to ensure that our study was not biased in favour of solid forms which readily form single crystals. A simplified reaction scheme is given in Scheme 1.
S2.HCl [(S)-phenylalanine methylamide hydrochloride] adopts the orthorhombic spacegroup P212121 with a single formula unit per asymmetric unit (Fig. 1a). All chemically intuitive hydrogen bonding opportunities are satisfied in the solid state (Fig. 2a). Sheets of hydrogen bonds are formed, which lie parallel to the ab plane. The chloride ion is hydrogen-bonded by three protonated amine groups [N16···Cl1 = 3.094 (2), 3.149 (2) and 3.166 (2) Å], and the carbonyl group of the amide unit is hydrogen bonded to the amide H atom on an adjacent molecule [N11···O10 = 3.018 (3) Å]. The hydrophobic (phenyl) and hydrophilic (amide) fragments of the molecule form layers, which are segregated along the c axis. Solid-state packing forces appear to have a slight influence on the molecular conformation; comparison of the observed molecular conformation with one computed using a gas-phase molecular mechanics model shows no unusual features, the two conformations being broadly similar. The primary differences arise because of a change in the C6—C7—C8—C9 torsion angle from 98.15° in the gas phase (calculated as described in the Experimental section) to 54.65° in the solid-state, which is presumably driven by a combination of crystal packing (optimal space filling) requirements and intermolecular hydrogen bonding of the amide group.
R3 and S3 [5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride] both crystallize in the orthorhombic space group P212121 with three formula units per asymmetric unit (S3 is shown in Fig. 1b). The three organic molecules adopt different but related conformations which differ primarily as a result of changes in the orientation of the imidazolidinone fragment with respect to the phenyl ring via C—C bond rotation. These differences in conformation do not affect the hydrogen-bonding topology, with all three organic cations forming two N—H···Cl hydrogen bonds from the protonated N atom to the free chloride ion (Fig. 2b). Neither the carbonyl nor the nitrogen of the amide group are involved in classical hydrogen bonding for any of the three distinct molecules, which is in contrast to the extensive hydrogen bonding observed for the precursor S2.HCl. Two of the three independent formula units are linked to each other by hydrogen bonding through Cl1 and Cl2 via N—H···Cl interactions and thereby form a chain of hydrogen bonds which runs parallel to the a axis. The third symmetry-independent formula unit again forms N—H···Cl hydrogen bonds to create a chain that runs parallel to both the a axis and the other hydrogen-bonding chain, but in this case the chain comprises only a single symmetry-independent molecule and a single symmetry-independent chloride ion (Cl1). The hydrophilic sections of the structure (Cl- ions and the polar parts of the organic cation) are layered in the ac plane and are separated by the hydrophobic phenyl rings. As expected, no significant differences exist between the crystal packing of the (R) and (S) isomers.
The presence of three formula units with different molecular conformations in the asymmetric unit is curious, and could result from either different minima on the molecular energy surface or distortions away from the same minimum caused by differences in packing forces experienced by the three independent molecules in the unit cell. To distinguish between these possibilities, we have performed calculations designed to elucidate the gas-phase conformers and their relative energies. R3 and S3 have two torsional degrees of freedom, which we label ϕ (torsion angle C6—C7—C8—C9) and θ (torsion angle C5—C6—C7—C8). Initial low-level calculations (using the molecular mechanics model Tripos 5.2) indicate that three distinct conformational energy minima exist in the gas phase (Fig. 3). The three minima were then re-optimized at higher levels of theory for more reliable relative energies, revealing large energy differences between the conformations: the relative energies are 0, +10.67 [+11.29], +32.57 [+33.95] kJ mol-1 for conformations i, ii and iii, respectively, at the B3LYP/6–31 G(d,p) [B3LYP/6–311 G(d,p)] levels. The good quantitative agreement between the two methods indicates that the effects of basis set superposition error on the relative conformational energies is small, while the stability of the most folded conformation i might even be underestimated owing to the known poor treatment of nonbonded interactions in density functional theory calculations (van Mourik et al., 2006). As typical energy differences between polymorphs are of the order of 1–10 kJ mol-1 (Bernstein, 2002), we might only expect the lowest energy conformation to be observed in the crystal structure. However, it is clear from Fig. 3 that two molecules (A and C) adopt conformations related to the intermediate-energy calculated conformation ii, while molecule (B) is within the potential energy well of the highest-energy calculated conformation iii, although significantly distorted away from the minimum. It therefore appears that in order to optimize the lattice energy, the three molecules avoid the lowest-energy, folded gas-phase conformation in favor of the two open conformations. The conformational energy penalty of at least 18 kJ mol-1 (2 × 11 kJ mol-1 for A and C, 33 kJ mol-1 for B) is presumably compensated by the formation of hydrogen bonds and van der Waals interactions in the crystal.
Both R4 and S4 [5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride hydrate] crystallize in the noncentrosymmetric monoclinic space group P21 with a single formula unit per asymmetric unit (S4 is shown in Fig. 1c). The conformation of the cation (θ = 109.3°, ϕ = 173.4°) corresponds most closely with minimum ii (Fig. 3), and it therefore appears that, as with R3 and S3, intermolecular factors including hydrogen bonding and van der Waals interactions outweigh intramolecular ones in determining the conformation of the cation in the solid state. Overall the hydrogen bonding leads to the formation of tapes which run parallel to the b axis (Fig. 2c). Again, the hydrophobic and hydrophilic parts of the structure are segregated into chains which follow the hydrogen-bonding topology. Again, no unexpected differences exist between the crystal packing of the (R) and (S) isomers.
In conclusion, computational and experimental studies indicate that intermolecular rather than intramolecular forces are primarily responsible for the molecular conformations observed in the solid state for this class of compounds.