Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107019506/ln3045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107019506/ln3045IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107019506/ln3045I_IIsup3.hkl |
CCDC references: 652513; 652514
For related literature, see: Allen (2002); Haynes & Pett (2007); Reinheimer et al. (1980, 1984); Van der Plas (1978).
The original samples of the intermediates as their sodium salts were prepared by following the directions of Reinheimer et al. (1980, 1984). Because of what appeared to be oxidation of the intermediate, one reaction of 2-chloro-5-nitropyridine with sodium hydroxide was carried out in a nitrogen atmosphere. Interestingly, the intermediate formed was (II). That reaction provided the sample of (II) that was used for the crystal structure determination. To produce crystalline material suitable for the vapor diffusion process, tetra-n-butylammonium bromide was added to an aqueous or water/dimethyl sulfoxide solution of the sodium salt. After freeze-drying to remove solvent(s), the tetra-n-butylammonium salt of the intermediate was separated from inorganic salts by extraction with acetone. Evaporation of the acetone gave a solid suitable for crystallization. 1H NMR: pseudo-cis (I) (D2O/D6DMSO): δ 9.75, 6.97, 5.23; pseudo-trans (II) (D2O/D6DMSO): δ 9.80, 7.37, 6.20. Suitable crystals of the tetra-n-butylammonium salts of the mixture of both intermediates were grown by vapor diffusion of hexanes into dichloromethane solutions of the intermediates.
The crystals grown from the original sample exhibit a disorder of the major pseudo-cis intermediate, (I), with a minor presence of the pseudo-trans isomer, (II). The data of several crystals were collected (only the best data set is reported here) and all structures exhibited similar pseudo-cis to pseudo-trans ratios [0.917 (3) to 0.083 (3) for the reported example]. The bond distances within the minor component were restrained to be the same as those of the major component (within a standard deviation of 0.02 Å), and the anisotropic displacement parameters of the minor component atoms were set to be the same as those of the major isomer. Atom C19, which by itself is not disordered, was included in the disorder but the major and minor component atoms were set to have the same coordinates and anisotropic displacement parameters, thus allowing us to add H19 and H19B in calculated positions rather than refining their positions using constraints. In both structures, all H atoms were placed in calculated positions with C—H distances of 0.98, 0.99 and 0.95 Å for methyl, methylene and alkene H atoms, respectively, and were refined with an isotropic displacement parameter of 1.5 (methyl) or 1.2 (methylene, alkene) times Ueq of the adjacent C atom. Methyl H atoms were allowed to rotate to best fit the experimental electron density.
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C16H36N+·C5H3N2O3− | F(000) = 840 |
Mr = 381.55 | Dx = 1.158 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.2793 (16) Å | Cell parameters from 6428 reflections |
b = 9.7588 (12) Å | θ = 2.7–30.6° |
c = 18.422 (2) Å | µ = 0.08 mm−1 |
β = 97.444 (2)° | T = 100 K |
V = 2189.0 (5) Å3 | Block, colourless |
Z = 4 | 0.6 × 0.4 × 0.25 mm |
Bruker SMART APEX CCD diffractometer | 5406 independent reflections |
Radiation source: fine-focus sealed tube | 4323 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −16→16 |
Tmin = 0.848, Tmax = 0.981 | k = −13→13 |
21198 measured reflections | l = −24→23 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0476P)2 + 2.9417P] where P = (Fo2 + 2Fc2)/3 |
5406 reflections | (Δ/σ)max < 0.001 |
258 parameters | Δρmax = 0.46 e Å−3 |
3 restraints | Δρmin = −0.22 e Å−3 |
C16H36N+·C5H3N2O3− | V = 2189.0 (5) Å3 |
Mr = 381.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.2793 (16) Å | µ = 0.08 mm−1 |
b = 9.7588 (12) Å | T = 100 K |
c = 18.422 (2) Å | 0.6 × 0.4 × 0.25 mm |
β = 97.444 (2)° |
Bruker SMART APEX CCD diffractometer | 5406 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 4323 reflections with I > 2σ(I) |
Tmin = 0.848, Tmax = 0.981 | Rint = 0.047 |
21198 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 3 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.46 e Å−3 |
5406 reflections | Δρmin = −0.22 e Å−3 |
258 parameters |
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 | Occ. (<1) | |
C1 | 0.66758 (17) | 0.4305 (2) | 0.51970 (11) | 0.0177 (4) | |
H1A | 0.6227 | 0.4714 | 0.5550 | 0.021* | |
H1B | 0.6172 | 0.4070 | 0.4750 | 0.021* | |
C2 | 0.71834 (17) | 0.2987 (2) | 0.55253 (12) | 0.0198 (4) | |
H2A | 0.7618 | 0.3179 | 0.6006 | 0.024* | |
H2B | 0.7680 | 0.2591 | 0.5198 | 0.024* | |
C3 | 0.62603 (18) | 0.1977 (2) | 0.56196 (12) | 0.0225 (4) | |
H3A | 0.5743 | 0.2410 | 0.5920 | 0.027* | |
H3B | 0.5851 | 0.1767 | 0.5133 | 0.027* | |
C4 | 0.6689 (2) | 0.0647 (2) | 0.59833 (13) | 0.0277 (5) | |
H4B | 0.7051 | 0.0842 | 0.6478 | 0.042* | |
H4C | 0.7216 | 0.0226 | 0.5695 | 0.042* | |
H4A | 0.6074 | 0.0017 | 0.6011 | 0.042* | |
C5 | 0.82398 (17) | 0.5857 (2) | 0.56707 (11) | 0.0180 (4) | |
H5A | 0.8645 | 0.5051 | 0.5892 | 0.022* | |
H5B | 0.8786 | 0.6499 | 0.5511 | 0.022* | |
C6 | 0.76742 (18) | 0.6557 (2) | 0.62561 (12) | 0.0220 (4) | |
H6A | 0.7154 | 0.5910 | 0.6442 | 0.026* | |
H6B | 0.7250 | 0.7354 | 0.6041 | 0.026* | |
C7 | 0.85114 (18) | 0.7034 (2) | 0.68867 (12) | 0.0244 (5) | |
H7B | 0.9104 | 0.7548 | 0.6690 | 0.029* | |
H7A | 0.8845 | 0.6226 | 0.7154 | 0.029* | |
C8 | 0.7982 (2) | 0.7949 (2) | 0.74164 (12) | 0.0259 (5) | |
H8B | 0.7385 | 0.7449 | 0.7604 | 0.039* | |
H8C | 0.7687 | 0.8775 | 0.7160 | 0.039* | |
H8A | 0.8534 | 0.8210 | 0.7826 | 0.039* | |
C9 | 0.67666 (17) | 0.6553 (2) | 0.46563 (11) | 0.0174 (4) | |
H9A | 0.6309 | 0.6200 | 0.4214 | 0.021* | |
H9B | 0.6263 | 0.6836 | 0.5007 | 0.021* | |
C10 | 0.73768 (17) | 0.7814 (2) | 0.44421 (12) | 0.0194 (4) | |
H10A | 0.7813 | 0.7581 | 0.4043 | 0.023* | |
H10B | 0.7887 | 0.8141 | 0.4867 | 0.023* | |
C11 | 0.65515 (18) | 0.8942 (2) | 0.41870 (12) | 0.0205 (4) | |
H11A | 0.6056 | 0.8616 | 0.3755 | 0.025* | |
H11B | 0.6098 | 0.9141 | 0.4581 | 0.025* | |
C12 | 0.7123 (2) | 1.0254 (2) | 0.39888 (13) | 0.0253 (5) | |
H12B | 0.7546 | 1.0069 | 0.3584 | 0.038* | |
H12C | 0.7618 | 1.0575 | 0.4415 | 0.038* | |
H12A | 0.6570 | 1.0959 | 0.3840 | 0.038* | |
C13 | 0.82321 (17) | 0.4830 (2) | 0.44702 (11) | 0.0185 (4) | |
H13A | 0.8703 | 0.5588 | 0.4337 | 0.022* | |
H13B | 0.8720 | 0.4131 | 0.4731 | 0.022* | |
C14 | 0.76606 (18) | 0.4194 (2) | 0.37688 (11) | 0.0201 (4) | |
H14A | 0.7269 | 0.4912 | 0.3458 | 0.024* | |
H14B | 0.7116 | 0.3509 | 0.3887 | 0.024* | |
C15 | 0.85185 (19) | 0.3506 (2) | 0.33596 (13) | 0.0257 (5) | |
H15A | 0.9051 | 0.4205 | 0.3238 | 0.031* | |
H15B | 0.8926 | 0.2819 | 0.3684 | 0.031* | |
C16 | 0.8011 (2) | 0.2806 (2) | 0.26595 (12) | 0.0278 (5) | |
H16B | 0.7615 | 0.3484 | 0.2333 | 0.042* | |
H16C | 0.7499 | 0.2095 | 0.2778 | 0.042* | |
H16A | 0.8592 | 0.2388 | 0.2416 | 0.042* | |
N1 | 0.74801 (14) | 0.53846 (17) | 0.49969 (9) | 0.0167 (3) | |
C17 | 0.50529 (19) | 0.8085 (2) | 0.77333 (13) | 0.0268 (5) | |
H17 | 0.5074 | 0.8763 | 0.7366 | 0.032* | |
C18 | 0.50457 (17) | 0.6675 (2) | 0.75225 (12) | 0.0212 (4) | |
N2 | 0.50543 (15) | 0.6390 (2) | 0.67769 (10) | 0.0243 (4) | |
O1 | 0.50716 (13) | 0.51655 (17) | 0.65574 (9) | 0.0273 (4) | |
O2 | 0.50433 (15) | 0.7341 (2) | 0.63188 (10) | 0.0343 (4) | |
O3 | 0.50335 (17) | 0.84590 (19) | 0.83661 (10) | 0.0389 (5) | |
C19 | 0.50129 (18) | 0.5527 (2) | 0.79985 (13) | 0.0237 (5) | 0.917 (3) |
H19 | 0.4973 | 0.4675 | 0.7746 | 0.028* | 0.917 (3) |
C20 | 0.5026 (5) | 0.5383 (4) | 0.87301 (15) | 0.0262 (7) | 0.917 (3) |
H20 | 0.4954 | 0.4462 | 0.8884 | 0.031* | 0.917 (3) |
C21 | 0.51271 (19) | 0.6356 (3) | 0.93144 (14) | 0.0240 (5) | 0.917 (3) |
N3 | 0.51927 (18) | 0.6968 (2) | 0.98476 (12) | 0.0290 (5) | 0.917 (3) |
C19B | 0.50129 (18) | 0.5527 (2) | 0.79985 (13) | 0.0237 (5) | 0.083 (3) |
H19B | 0.4882 | 0.4648 | 0.7783 | 0.028* | 0.083 (3) |
C20B | 0.516 (7) | 0.561 (4) | 0.8742 (10) | 0.0262 (7) | 0.083 (3) |
H20B | 0.5323 | 0.6467 | 0.8975 | 0.031* | 0.083 (3) |
C21B | 0.506 (2) | 0.440 (2) | 0.9173 (14) | 0.0240 (5) | 0.083 (3) |
N3B | 0.494 (2) | 0.341 (2) | 0.9503 (13) | 0.0290 (5) | 0.083 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0183 (10) | 0.0152 (9) | 0.0199 (9) | −0.0024 (8) | 0.0039 (7) | 0.0002 (7) |
C2 | 0.0213 (10) | 0.0146 (9) | 0.0235 (10) | −0.0009 (8) | 0.0034 (8) | 0.0014 (8) |
C3 | 0.0258 (11) | 0.0170 (10) | 0.0250 (11) | −0.0033 (8) | 0.0047 (8) | 0.0021 (8) |
C4 | 0.0367 (13) | 0.0186 (11) | 0.0282 (12) | −0.0045 (9) | 0.0054 (9) | 0.0032 (9) |
C5 | 0.0175 (9) | 0.0147 (9) | 0.0209 (10) | −0.0005 (7) | −0.0001 (7) | 0.0001 (8) |
C6 | 0.0209 (10) | 0.0216 (11) | 0.0235 (10) | 0.0001 (8) | 0.0026 (8) | −0.0031 (8) |
C7 | 0.0229 (11) | 0.0255 (11) | 0.0247 (11) | −0.0014 (9) | 0.0025 (8) | −0.0023 (9) |
C8 | 0.0302 (12) | 0.0250 (11) | 0.0223 (11) | −0.0007 (9) | 0.0030 (9) | −0.0037 (9) |
C9 | 0.0182 (9) | 0.0118 (9) | 0.0222 (10) | 0.0013 (7) | 0.0024 (7) | 0.0015 (7) |
C10 | 0.0202 (10) | 0.0148 (9) | 0.0234 (10) | 0.0004 (8) | 0.0039 (8) | 0.0019 (8) |
C11 | 0.0226 (10) | 0.0154 (10) | 0.0236 (10) | 0.0024 (8) | 0.0038 (8) | 0.0010 (8) |
C12 | 0.0311 (12) | 0.0154 (10) | 0.0306 (12) | 0.0011 (9) | 0.0081 (9) | 0.0023 (9) |
C13 | 0.0184 (10) | 0.0150 (9) | 0.0232 (10) | 0.0023 (8) | 0.0070 (8) | 0.0007 (8) |
C14 | 0.0223 (10) | 0.0171 (10) | 0.0215 (10) | 0.0021 (8) | 0.0054 (8) | 0.0000 (8) |
C15 | 0.0243 (11) | 0.0230 (11) | 0.0314 (12) | 0.0033 (9) | 0.0102 (9) | −0.0037 (9) |
C16 | 0.0379 (13) | 0.0243 (11) | 0.0224 (11) | 0.0048 (10) | 0.0086 (9) | 0.0005 (9) |
N1 | 0.0171 (8) | 0.0131 (8) | 0.0202 (8) | 0.0003 (6) | 0.0037 (6) | 0.0001 (6) |
C17 | 0.0276 (12) | 0.0184 (11) | 0.0328 (12) | 0.0019 (9) | −0.0018 (9) | −0.0011 (9) |
C18 | 0.0182 (10) | 0.0201 (10) | 0.0251 (10) | −0.0005 (8) | 0.0022 (8) | −0.0035 (8) |
N2 | 0.0187 (9) | 0.0264 (10) | 0.0273 (10) | 0.0022 (8) | 0.0018 (7) | −0.0007 (8) |
O1 | 0.0262 (8) | 0.0287 (9) | 0.0269 (8) | 0.0030 (7) | 0.0032 (6) | −0.0098 (7) |
O2 | 0.0344 (10) | 0.0357 (10) | 0.0325 (9) | 0.0041 (8) | 0.0038 (7) | 0.0058 (8) |
O3 | 0.0561 (13) | 0.0232 (9) | 0.0356 (10) | 0.0041 (8) | −0.0006 (9) | −0.0088 (8) |
C19 | 0.0233 (11) | 0.0177 (10) | 0.0305 (11) | −0.0010 (8) | 0.0052 (9) | −0.0057 (9) |
C20 | 0.029 (2) | 0.0205 (16) | 0.0301 (12) | −0.0035 (14) | 0.0070 (10) | −0.0040 (10) |
C21 | 0.0182 (11) | 0.0259 (12) | 0.0287 (13) | −0.0014 (9) | 0.0053 (9) | 0.0002 (10) |
N3 | 0.0256 (11) | 0.0319 (12) | 0.0298 (12) | −0.0029 (9) | 0.0043 (9) | −0.0071 (9) |
C19B | 0.0233 (11) | 0.0177 (10) | 0.0305 (11) | −0.0010 (8) | 0.0052 (9) | −0.0057 (9) |
C20B | 0.029 (2) | 0.0205 (16) | 0.0301 (12) | −0.0035 (14) | 0.0070 (10) | −0.0040 (10) |
C21B | 0.0182 (11) | 0.0259 (12) | 0.0287 (13) | −0.0014 (9) | 0.0053 (9) | 0.0002 (10) |
N3B | 0.0256 (11) | 0.0319 (12) | 0.0298 (12) | −0.0029 (9) | 0.0043 (9) | −0.0071 (9) |
C1—C2 | 1.520 (3) | C11—H11A | 0.9900 |
C1—N1 | 1.522 (3) | C11—H11B | 0.9900 |
C1—H1A | 0.9900 | C12—H12B | 0.9800 |
C1—H1B | 0.9900 | C12—H12C | 0.9800 |
C2—C3 | 1.529 (3) | C12—H12A | 0.9800 |
C2—H2A | 0.9900 | C13—C14 | 1.520 (3) |
C2—H2B | 0.9900 | C13—N1 | 1.523 (3) |
C3—C4 | 1.523 (3) | C13—H13A | 0.9900 |
C3—H3A | 0.9900 | C13—H13B | 0.9900 |
C3—H3B | 0.9900 | C14—C15 | 1.528 (3) |
C4—H4B | 0.9800 | C14—H14A | 0.9900 |
C4—H4C | 0.9800 | C14—H14B | 0.9900 |
C4—H4A | 0.9800 | C15—C16 | 1.520 (3) |
C5—C6 | 1.518 (3) | C15—H15A | 0.9900 |
C5—N1 | 1.524 (3) | C15—H15B | 0.9900 |
C5—H5A | 0.9900 | C16—H16B | 0.9800 |
C5—H5B | 0.9900 | C16—H16C | 0.9800 |
C6—C7 | 1.521 (3) | C16—H16A | 0.9800 |
C6—H6A | 0.9900 | C17—O3 | 1.225 (3) |
C6—H6B | 0.9900 | C17—C18 | 1.429 (3) |
C7—C8 | 1.529 (3) | C17—H17 | 0.9500 |
C7—H7B | 0.9900 | C18—N2 | 1.403 (3) |
C7—H7A | 0.9900 | C18—C19 | 1.427 (3) |
C8—H8B | 0.9800 | N2—O2 | 1.253 (3) |
C8—H8C | 0.9800 | N2—O1 | 1.263 (3) |
C8—H8A | 0.9800 | C19—C20 | 1.353 (4) |
C9—C10 | 1.520 (3) | C19—H19 | 0.9500 |
C9—N1 | 1.522 (3) | C20—C21 | 1.428 (4) |
C9—H9A | 0.9900 | C20—H20 | 0.9500 |
C9—H9B | 0.9900 | C21—N3 | 1.143 (3) |
C10—C11 | 1.528 (3) | C20B—C21B | 1.44 (2) |
C10—H10A | 0.9900 | C20B—H20B | 0.9500 |
C10—H10B | 0.9900 | C21B—N3B | 1.163 (18) |
C11—C12 | 1.527 (3) | ||
C2—C1—N1 | 115.89 (17) | C12—C11—C10 | 111.75 (18) |
C2—C1—H1A | 108.3 | C12—C11—H11A | 109.3 |
N1—C1—H1A | 108.3 | C10—C11—H11A | 109.3 |
C2—C1—H1B | 108.3 | C12—C11—H11B | 109.3 |
N1—C1—H1B | 108.3 | C10—C11—H11B | 109.3 |
H1A—C1—H1B | 107.4 | H11A—C11—H11B | 107.9 |
C1—C2—C3 | 108.59 (17) | C11—C12—H12B | 109.5 |
C1—C2—H2A | 110.0 | C11—C12—H12C | 109.5 |
C3—C2—H2A | 110.0 | H12B—C12—H12C | 109.5 |
C1—C2—H2B | 110.0 | C11—C12—H12A | 109.5 |
C3—C2—H2B | 110.0 | H12B—C12—H12A | 109.5 |
H2A—C2—H2B | 108.4 | H12C—C12—H12A | 109.5 |
C4—C3—C2 | 112.38 (19) | C14—C13—N1 | 115.80 (17) |
C4—C3—H3A | 109.1 | C14—C13—H13A | 108.3 |
C2—C3—H3A | 109.1 | N1—C13—H13A | 108.3 |
C4—C3—H3B | 109.1 | C14—C13—H13B | 108.3 |
C2—C3—H3B | 109.1 | N1—C13—H13B | 108.3 |
H3A—C3—H3B | 107.9 | H13A—C13—H13B | 107.4 |
C3—C4—H4B | 109.5 | C13—C14—C15 | 109.07 (18) |
C3—C4—H4C | 109.5 | C13—C14—H14A | 109.9 |
H4B—C4—H4C | 109.5 | C15—C14—H14A | 109.9 |
C3—C4—H4A | 109.5 | C13—C14—H14B | 109.9 |
H4B—C4—H4A | 109.5 | C15—C14—H14B | 109.9 |
H4C—C4—H4A | 109.5 | H14A—C14—H14B | 108.3 |
C6—C5—N1 | 115.24 (17) | C16—C15—C14 | 112.53 (19) |
C6—C5—H5A | 108.5 | C16—C15—H15A | 109.1 |
N1—C5—H5A | 108.5 | C14—C15—H15A | 109.1 |
C6—C5—H5B | 108.5 | C16—C15—H15B | 109.1 |
N1—C5—H5B | 108.5 | C14—C15—H15B | 109.1 |
H5A—C5—H5B | 107.5 | H15A—C15—H15B | 107.8 |
C5—C6—C7 | 110.73 (18) | C15—C16—H16B | 109.5 |
C5—C6—H6A | 109.5 | C15—C16—H16C | 109.5 |
C7—C6—H6A | 109.5 | H16B—C16—H16C | 109.5 |
C5—C6—H6B | 109.5 | C15—C16—H16A | 109.5 |
C7—C6—H6B | 109.5 | H16B—C16—H16A | 109.5 |
H6A—C6—H6B | 108.1 | H16C—C16—H16A | 109.5 |
C6—C7—C8 | 111.41 (19) | C1—N1—C9 | 105.15 (15) |
C6—C7—H7B | 109.3 | C1—N1—C13 | 111.98 (15) |
C8—C7—H7B | 109.3 | C9—N1—C13 | 111.56 (15) |
C6—C7—H7A | 109.3 | C1—N1—C5 | 111.12 (15) |
C8—C7—H7A | 109.3 | C9—N1—C5 | 111.58 (15) |
H7B—C7—H7A | 108.0 | C13—N1—C5 | 105.59 (15) |
C7—C8—H8B | 109.5 | O3—C17—C18 | 123.1 (2) |
C7—C8—H8C | 109.5 | O3—C17—H17 | 118.5 |
H8B—C8—H8C | 109.5 | C18—C17—H17 | 118.5 |
C7—C8—H8A | 109.5 | N2—C18—C19 | 116.78 (19) |
H8B—C8—H8A | 109.5 | N2—C18—C17 | 117.1 (2) |
H8C—C8—H8A | 109.5 | C19—C18—C17 | 126.1 (2) |
C10—C9—N1 | 115.90 (17) | O2—N2—O1 | 118.96 (19) |
C10—C9—H9A | 108.3 | O2—N2—C18 | 120.8 (2) |
N1—C9—H9A | 108.3 | O1—N2—C18 | 120.24 (19) |
C10—C9—H9B | 108.3 | C20—C19—C18 | 134.1 (2) |
N1—C9—H9B | 108.3 | C20—C19—H19 | 113.0 |
H9A—C9—H9B | 107.4 | C18—C19—H19 | 113.0 |
C9—C10—C11 | 109.49 (17) | C19—C20—C21 | 132.1 (3) |
C9—C10—H10A | 109.8 | C19—C20—H20 | 113.9 |
C11—C10—H10A | 109.8 | C21—C20—H20 | 113.9 |
C9—C10—H10B | 109.8 | N3—C21—C20 | 169.7 (3) |
C11—C10—H10B | 109.8 | C21B—C20B—H20B | 120.0 |
H10A—C10—H10B | 108.2 | N3B—C21B—C20B | 177 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···N3i | 0.95 | 2.75 | 3.519 (4) | 139 |
C20B—H20B···N3Bi | 0.95 | 2.87 | 3.39 (4) | 116 |
C20B—H20B···O3 | 0.95 | 2.25 | 2.86 (4) | 122 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
C16H36N+·C5H3N2O3− | F(000) = 840 |
Mr = 381.55 | Dx = 1.157 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7894 (9) Å | Cell parameters from 7740 reflections |
b = 18.3872 (16) Å | θ = 2.5–30.5° |
c = 12.2327 (11) Å | µ = 0.08 mm−1 |
β = 95.894 (2)° | T = 100 K |
V = 2190.2 (3) Å3 | Plate, yellow |
Z = 4 | 0.73 × 0.59 × 0.10 mm |
Bruker SMART APEX CCD diffractometer | 5402 independent reflections |
Radiation source: fine-focus sealed tube | 4809 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −12→12 |
Tmin = 0.792, Tmax = 0.992 | k = −24→24 |
18699 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.046P)2 + 1.24P] where P = (Fo2 + 2Fc2)/3 |
5402 reflections | (Δ/σ)max < 0.001 |
248 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C16H36N+·C5H3N2O3− | V = 2190.2 (3) Å3 |
Mr = 381.55 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7894 (9) Å | µ = 0.08 mm−1 |
b = 18.3872 (16) Å | T = 100 K |
c = 12.2327 (11) Å | 0.73 × 0.59 × 0.10 mm |
β = 95.894 (2)° |
Bruker SMART APEX CCD diffractometer | 5402 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 4809 reflections with I > 2σ(I) |
Tmin = 0.792, Tmax = 0.992 | Rint = 0.033 |
18699 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.40 e Å−3 |
5402 reflections | Δρmin = −0.18 e Å−3 |
248 parameters |
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 | ||
C1 | 0.63204 (14) | 0.54280 (8) | 0.32202 (11) | 0.0164 (3) | |
H1A | 0.6031 | 0.5820 | 0.3702 | 0.020* | |
H1B | 0.6666 | 0.5020 | 0.3700 | 0.020* | |
C2 | 0.74961 (15) | 0.57108 (8) | 0.26236 (12) | 0.0183 (3) | |
H2A | 0.7195 | 0.6144 | 0.2183 | 0.022* | |
H2B | 0.7786 | 0.5333 | 0.2119 | 0.022* | |
C3 | 0.87024 (15) | 0.59110 (8) | 0.34724 (12) | 0.0189 (3) | |
H3A | 0.8392 | 0.6276 | 0.3988 | 0.023* | |
H3B | 0.9001 | 0.5473 | 0.3902 | 0.023* | |
C4 | 0.99152 (16) | 0.62164 (9) | 0.29370 (14) | 0.0248 (3) | |
H4A | 1.0225 | 0.5857 | 0.2425 | 0.037* | |
H4B | 1.0667 | 0.6326 | 0.3505 | 0.037* | |
H4C | 0.9635 | 0.6662 | 0.2536 | 0.037* | |
C5 | 0.44491 (15) | 0.57737 (8) | 0.17477 (12) | 0.0169 (3) | |
H5A | 0.5166 | 0.5953 | 0.1300 | 0.020* | |
H5B | 0.3698 | 0.5568 | 0.1237 | 0.020* | |
C6 | 0.38857 (15) | 0.64184 (8) | 0.23411 (12) | 0.0187 (3) | |
H6A | 0.4632 | 0.6642 | 0.2837 | 0.022* | |
H6B | 0.3166 | 0.6249 | 0.2794 | 0.022* | |
C7 | 0.32799 (17) | 0.69845 (8) | 0.15138 (12) | 0.0216 (3) | |
H7A | 0.4032 | 0.7213 | 0.1153 | 0.026* | |
H7B | 0.2659 | 0.6739 | 0.0939 | 0.026* | |
C8 | 0.24848 (16) | 0.75733 (8) | 0.20554 (13) | 0.0227 (3) | |
H8A | 0.1708 | 0.7353 | 0.2378 | 0.034* | |
H8B | 0.2143 | 0.7933 | 0.1503 | 0.034* | |
H8C | 0.3092 | 0.7813 | 0.2633 | 0.034* | |
C9 | 0.40544 (14) | 0.49097 (8) | 0.32781 (11) | 0.0162 (3) | |
H9A | 0.4496 | 0.4514 | 0.3736 | 0.019* | |
H9B | 0.3888 | 0.5318 | 0.3776 | 0.019* | |
C10 | 0.26728 (15) | 0.46365 (8) | 0.27566 (12) | 0.0187 (3) | |
H10A | 0.2796 | 0.4184 | 0.2338 | 0.022* | |
H10B | 0.2239 | 0.5006 | 0.2244 | 0.022* | |
C11 | 0.17640 (16) | 0.44895 (8) | 0.36777 (13) | 0.0209 (3) | |
H11A | 0.2244 | 0.4147 | 0.4211 | 0.025* | |
H11B | 0.1625 | 0.4950 | 0.4070 | 0.025* | |
C12 | 0.03667 (16) | 0.41727 (9) | 0.32632 (15) | 0.0262 (3) | |
H12A | −0.0108 | 0.4505 | 0.2724 | 0.039* | |
H12B | −0.0183 | 0.4109 | 0.3882 | 0.039* | |
H12C | 0.0493 | 0.3700 | 0.2916 | 0.039* | |
C13 | 0.54293 (15) | 0.45516 (8) | 0.17377 (12) | 0.0173 (3) | |
H13A | 0.4571 | 0.4361 | 0.1341 | 0.021* | |
H13B | 0.5991 | 0.4755 | 0.1183 | 0.021* | |
C14 | 0.62082 (16) | 0.39207 (8) | 0.23095 (12) | 0.0212 (3) | |
H14A | 0.5679 | 0.3725 | 0.2891 | 0.025* | |
H14B | 0.7104 | 0.4095 | 0.2662 | 0.025* | |
C15 | 0.64426 (17) | 0.33200 (8) | 0.14898 (13) | 0.0226 (3) | |
H15A | 0.5575 | 0.3049 | 0.1308 | 0.027* | |
H15B | 0.6704 | 0.3542 | 0.0804 | 0.027* | |
C16 | 0.75587 (17) | 0.27925 (9) | 0.19360 (15) | 0.0268 (3) | |
H16A | 0.8427 | 0.3055 | 0.2095 | 0.040* | |
H16B | 0.7668 | 0.2413 | 0.1389 | 0.040* | |
H16C | 0.7301 | 0.2569 | 0.2612 | 0.040* | |
N1 | 0.50602 (12) | 0.51662 (6) | 0.24910 (9) | 0.0153 (2) | |
C17 | 0.20257 (17) | 0.77034 (9) | 0.50905 (13) | 0.0254 (3) | |
H17 | 0.1375 | 0.7324 | 0.5134 | 0.030* | |
C18 | 0.34253 (16) | 0.75045 (8) | 0.50268 (12) | 0.0203 (3) | |
C19 | 0.45254 (16) | 0.80048 (8) | 0.49434 (12) | 0.0202 (3) | |
H19 | 0.5414 | 0.7803 | 0.4912 | 0.024* | |
N2 | 0.37436 (14) | 0.67619 (7) | 0.50370 (10) | 0.0214 (3) | |
O1 | 0.49752 (12) | 0.65604 (6) | 0.50463 (9) | 0.0251 (3) | |
O2 | 0.28071 (13) | 0.62929 (6) | 0.50371 (10) | 0.0289 (3) | |
O3 | 0.16086 (12) | 0.83358 (7) | 0.50927 (11) | 0.0317 (3) | |
C20 | 0.44254 (16) | 0.87390 (8) | 0.49049 (13) | 0.0225 (3) | |
H20 | 0.3557 | 0.8965 | 0.4936 | 0.027* | |
C21 | 0.56115 (17) | 0.91752 (9) | 0.48180 (13) | 0.0244 (3) | |
N3 | 0.65593 (16) | 0.95393 (8) | 0.47543 (13) | 0.0312 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0139 (6) | 0.0180 (7) | 0.0169 (6) | −0.0007 (5) | −0.0006 (5) | −0.0018 (5) |
C2 | 0.0161 (7) | 0.0200 (7) | 0.0189 (7) | −0.0029 (5) | 0.0015 (5) | 0.0007 (5) |
C3 | 0.0158 (7) | 0.0202 (7) | 0.0203 (7) | −0.0012 (5) | −0.0003 (5) | −0.0001 (5) |
C4 | 0.0174 (7) | 0.0287 (8) | 0.0281 (8) | −0.0041 (6) | 0.0007 (6) | 0.0028 (6) |
C5 | 0.0168 (7) | 0.0162 (7) | 0.0174 (6) | 0.0002 (5) | 0.0001 (5) | 0.0032 (5) |
C6 | 0.0199 (7) | 0.0170 (7) | 0.0191 (7) | 0.0007 (5) | 0.0008 (5) | 0.0012 (5) |
C7 | 0.0257 (8) | 0.0182 (7) | 0.0204 (7) | 0.0024 (6) | −0.0008 (6) | 0.0023 (5) |
C8 | 0.0245 (8) | 0.0163 (7) | 0.0271 (8) | 0.0004 (6) | 0.0019 (6) | 0.0018 (6) |
C9 | 0.0153 (7) | 0.0165 (6) | 0.0171 (6) | −0.0009 (5) | 0.0035 (5) | 0.0016 (5) |
C10 | 0.0164 (7) | 0.0189 (7) | 0.0209 (7) | −0.0026 (5) | 0.0020 (5) | 0.0002 (5) |
C11 | 0.0186 (7) | 0.0210 (7) | 0.0237 (7) | −0.0019 (6) | 0.0051 (6) | 0.0005 (6) |
C12 | 0.0191 (8) | 0.0246 (8) | 0.0355 (9) | −0.0029 (6) | 0.0063 (6) | −0.0024 (7) |
C13 | 0.0176 (7) | 0.0173 (7) | 0.0171 (7) | 0.0006 (5) | 0.0017 (5) | −0.0027 (5) |
C14 | 0.0244 (8) | 0.0194 (7) | 0.0198 (7) | 0.0048 (6) | 0.0017 (6) | −0.0011 (6) |
C15 | 0.0255 (8) | 0.0177 (7) | 0.0246 (7) | −0.0008 (6) | 0.0027 (6) | −0.0036 (6) |
C16 | 0.0249 (8) | 0.0190 (7) | 0.0366 (9) | 0.0011 (6) | 0.0037 (7) | −0.0049 (6) |
N1 | 0.0137 (6) | 0.0157 (6) | 0.0166 (6) | −0.0004 (4) | 0.0014 (4) | −0.0003 (4) |
C17 | 0.0218 (8) | 0.0293 (8) | 0.0248 (8) | −0.0013 (6) | 0.0009 (6) | −0.0062 (6) |
C18 | 0.0225 (8) | 0.0205 (7) | 0.0175 (7) | 0.0023 (6) | −0.0005 (5) | −0.0021 (5) |
C19 | 0.0202 (7) | 0.0240 (7) | 0.0163 (7) | 0.0038 (6) | 0.0011 (5) | −0.0015 (5) |
N2 | 0.0275 (7) | 0.0211 (6) | 0.0150 (6) | 0.0012 (5) | −0.0001 (5) | −0.0012 (5) |
O1 | 0.0278 (6) | 0.0212 (5) | 0.0257 (6) | 0.0073 (5) | 0.0006 (5) | −0.0014 (4) |
O2 | 0.0343 (7) | 0.0237 (6) | 0.0281 (6) | −0.0067 (5) | −0.0006 (5) | −0.0016 (5) |
O3 | 0.0219 (6) | 0.0317 (6) | 0.0408 (7) | 0.0068 (5) | −0.0006 (5) | −0.0092 (5) |
C20 | 0.0208 (7) | 0.0226 (7) | 0.0238 (7) | 0.0031 (6) | 0.0010 (6) | −0.0011 (6) |
C21 | 0.0269 (8) | 0.0196 (7) | 0.0265 (8) | 0.0064 (6) | 0.0015 (6) | 0.0002 (6) |
N3 | 0.0269 (8) | 0.0227 (7) | 0.0439 (9) | 0.0023 (6) | 0.0038 (6) | 0.0027 (6) |
C1—C2 | 1.517 (2) | C10—H10B | 0.9900 |
C1—N1 | 1.5243 (17) | C11—C12 | 1.525 (2) |
C1—H1A | 0.9900 | C11—H11A | 0.9900 |
C1—H1B | 0.9900 | C11—H11B | 0.9900 |
C2—C3 | 1.5350 (19) | C12—H12A | 0.9800 |
C2—H2A | 0.9900 | C12—H12B | 0.9800 |
C2—H2B | 0.9900 | C12—H12C | 0.9800 |
C3—C4 | 1.521 (2) | C13—C14 | 1.519 (2) |
C3—H3A | 0.9900 | C13—N1 | 1.5248 (18) |
C3—H3B | 0.9900 | C13—H13A | 0.9900 |
C4—H4A | 0.9800 | C13—H13B | 0.9900 |
C4—H4B | 0.9800 | C14—C15 | 1.525 (2) |
C4—H4C | 0.9800 | C14—H14A | 0.9900 |
C5—C6 | 1.523 (2) | C14—H14B | 0.9900 |
C5—N1 | 1.5233 (17) | C15—C16 | 1.520 (2) |
C5—H5A | 0.9900 | C15—H15A | 0.9900 |
C5—H5B | 0.9900 | C15—H15B | 0.9900 |
C6—C7 | 1.528 (2) | C16—H16A | 0.9800 |
C6—H6A | 0.9900 | C16—H16B | 0.9800 |
C6—H6B | 0.9900 | C16—H16C | 0.9800 |
C7—C8 | 1.524 (2) | C17—O3 | 1.233 (2) |
C7—H7A | 0.9900 | C17—C18 | 1.428 (2) |
C7—H7B | 0.9900 | C17—H17 | 0.9500 |
C8—H8A | 0.9800 | C18—N2 | 1.400 (2) |
C8—H8B | 0.9800 | C18—C19 | 1.428 (2) |
C8—H8C | 0.9800 | C19—C20 | 1.354 (2) |
C9—C10 | 1.5203 (19) | C19—H19 | 0.9500 |
C9—N1 | 1.5211 (18) | N2—O2 | 1.2586 (18) |
C9—H9A | 0.9900 | N2—O1 | 1.2602 (18) |
C9—H9B | 0.9900 | C20—C21 | 1.424 (2) |
C10—C11 | 1.530 (2) | C20—H20 | 0.9500 |
C10—H10A | 0.9900 | C21—N3 | 1.153 (2) |
C2—C1—N1 | 115.80 (11) | H10A—C10—H10B | 108.4 |
C2—C1—H1A | 108.3 | C12—C11—C10 | 113.10 (13) |
N1—C1—H1A | 108.3 | C12—C11—H11A | 109.0 |
C2—C1—H1B | 108.3 | C10—C11—H11A | 109.0 |
N1—C1—H1B | 108.3 | C12—C11—H11B | 109.0 |
H1A—C1—H1B | 107.4 | C10—C11—H11B | 109.0 |
C1—C2—C3 | 109.02 (12) | H11A—C11—H11B | 107.8 |
C1—C2—H2A | 109.9 | C11—C12—H12A | 109.5 |
C3—C2—H2A | 109.9 | C11—C12—H12B | 109.5 |
C1—C2—H2B | 109.9 | H12A—C12—H12B | 109.5 |
C3—C2—H2B | 109.9 | C11—C12—H12C | 109.5 |
H2A—C2—H2B | 108.3 | H12A—C12—H12C | 109.5 |
C4—C3—C2 | 112.18 (12) | H12B—C12—H12C | 109.5 |
C4—C3—H3A | 109.2 | C14—C13—N1 | 115.26 (11) |
C2—C3—H3A | 109.2 | C14—C13—H13A | 108.5 |
C4—C3—H3B | 109.2 | N1—C13—H13A | 108.5 |
C2—C3—H3B | 109.2 | C14—C13—H13B | 108.5 |
H3A—C3—H3B | 107.9 | N1—C13—H13B | 108.5 |
C3—C4—H4A | 109.5 | H13A—C13—H13B | 107.5 |
C3—C4—H4B | 109.5 | C13—C14—C15 | 110.65 (12) |
H4A—C4—H4B | 109.5 | C13—C14—H14A | 109.5 |
C3—C4—H4C | 109.5 | C15—C14—H14A | 109.5 |
H4A—C4—H4C | 109.5 | C13—C14—H14B | 109.5 |
H4B—C4—H4C | 109.5 | C15—C14—H14B | 109.5 |
C6—C5—N1 | 115.19 (11) | H14A—C14—H14B | 108.1 |
C6—C5—H5A | 108.5 | C16—C15—C14 | 112.16 (13) |
N1—C5—H5A | 108.5 | C16—C15—H15A | 109.2 |
C6—C5—H5B | 108.5 | C14—C15—H15A | 109.2 |
N1—C5—H5B | 108.5 | C16—C15—H15B | 109.2 |
H5A—C5—H5B | 107.5 | C14—C15—H15B | 109.2 |
C5—C6—C7 | 110.46 (12) | H15A—C15—H15B | 107.9 |
C5—C6—H6A | 109.6 | C15—C16—H16A | 109.5 |
C7—C6—H6A | 109.6 | C15—C16—H16B | 109.5 |
C5—C6—H6B | 109.6 | H16A—C16—H16B | 109.5 |
C7—C6—H6B | 109.6 | C15—C16—H16C | 109.5 |
H6A—C6—H6B | 108.1 | H16A—C16—H16C | 109.5 |
C8—C7—C6 | 112.13 (13) | H16B—C16—H16C | 109.5 |
C8—C7—H7A | 109.2 | C9—N1—C5 | 111.42 (11) |
C6—C7—H7A | 109.2 | C9—N1—C1 | 105.37 (10) |
C8—C7—H7B | 109.2 | C5—N1—C1 | 111.25 (10) |
C6—C7—H7B | 109.2 | C9—N1—C13 | 111.21 (11) |
H7A—C7—H7B | 107.9 | C5—N1—C13 | 106.60 (10) |
C7—C8—H8A | 109.5 | C1—N1—C13 | 111.10 (11) |
C7—C8—H8B | 109.5 | O3—C17—C18 | 124.18 (16) |
H8A—C8—H8B | 109.5 | O3—C17—H17 | 117.9 |
C7—C8—H8C | 109.5 | C18—C17—H17 | 117.9 |
H8A—C8—H8C | 109.5 | N2—C18—C17 | 117.60 (14) |
H8B—C8—H8C | 109.5 | N2—C18—C19 | 117.39 (14) |
C10—C9—N1 | 116.27 (11) | C17—C18—C19 | 125.01 (14) |
C10—C9—H9A | 108.2 | C20—C19—C18 | 126.33 (15) |
N1—C9—H9A | 108.2 | C20—C19—H19 | 116.8 |
C10—C9—H9B | 108.2 | C18—C19—H19 | 116.8 |
N1—C9—H9B | 108.2 | O2—N2—O1 | 119.66 (13) |
H9A—C9—H9B | 107.4 | O2—N2—C18 | 120.44 (13) |
C9—C10—C11 | 107.99 (12) | O1—N2—C18 | 119.90 (13) |
C9—C10—H10A | 110.1 | C19—C20—C21 | 120.49 (15) |
C11—C10—H10A | 110.1 | C19—C20—H20 | 119.8 |
C9—C10—H10B | 110.1 | C21—C20—H20 | 119.8 |
C11—C10—H10B | 110.1 | N3—C21—C20 | 178.74 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···N3i | 0.95 | 2.78 | 3.348 (2) | 119 |
C20—H20···O3 | 0.95 | 2.26 | 2.887 (2) | 123 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
(I_II) | (II) | |
Crystal data | ||
Chemical formula | C16H36N+·C5H3N2O3− | C16H36N+·C5H3N2O3− |
Mr | 381.55 | 381.55 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 12.2793 (16), 9.7588 (12), 18.422 (2) | 9.7894 (9), 18.3872 (16), 12.2327 (11) |
β (°) | 97.444 (2) | 95.894 (2) |
V (Å3) | 2189.0 (5) | 2190.2 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.6 × 0.4 × 0.25 | 0.73 × 0.59 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) |
Tmin, Tmax | 0.848, 0.981 | 0.792, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21198, 5406, 4323 | 18699, 5402, 4809 |
Rint | 0.047 | 0.033 |
(sin θ/λ)max (Å−1) | 0.667 | 0.667 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.175, 1.13 | 0.058, 0.136, 1.19 |
No. of reflections | 5406 | 5402 |
No. of parameters | 258 | 248 |
No. of restraints | 3 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.22 | 0.40, −0.18 |
Computer programs: SMART (Bruker, 1997), SAINT-Plus (Bruker, 2003), SAINT-Plus, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···N3i | 0.95 | 2.75 | 3.519 (4) | 139 |
C20B—H20B···N3Bi | 0.95 | 2.87 | 3.39 (4) | 116 |
C20B—H20B···O3 | 0.95 | 2.25 | 2.86 (4) | 122 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···N3i | 0.95 | 2.78 | 3.348 (2) | 119 |
C20—H20···O3 | 0.95 | 2.26 | 2.887 (2) | 123 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Compound | (I)a | (II)b | (II)c | (III)d |
O3—C17 | 1.225 (3) | 1.233 (2) | 1.225 (3) | 1.249 (3) |
C17—C18 | 1.429 (3) | 1.428 (2) | 1.429 (3) | 1.421 (3) |
C18—C19 | 1.427 (3) | 1.428 (2) | 1.427 (3) | 1.361 (3) |
C19—C20 | 1.353 (4) | 1.354 (2) | 1.353 (4) | 1.408 (3) |
C20—C21 | 1.428 (4) | 1.424 (2) | 1.44 (2) | 1.418 (3) |
C18—N2 | 1.403 (3) | 1.400 (2) | 1.403 (3) | 1.378 (3) |
C21—N3 | 1.143 (3) | 1.153 (2) | 1.163 (18) | 1.150 (3) |
N2—O1 | 1.263 (3) | 1.2602 (18) | 1.263 (3) | 1.246 (2) |
N2—O2 | 1.253 (3) | 1.2586 (18) | 1.253 (3) | 1.264 (3) |
Notes: (a) this work, pseudo-cis isomer, cocrystallized sample (I/II); (b) this work, pure pseudo-trans sample (II); (c) this work, pseudo-trans isomer, cocrystallized sample (I/II); (d) Haynes & Pett (2007), (III); the same atom numbering as in samples (I/II) and (II) is used here for consistency. |
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During the 1980 s, Reinheimer et al. (1980, 1984) investigated the reaction of 2-chloro-5-nitropyridine with an excess of sodium hydroxide in dimethyl sulfoxide/water solutions. Using visible spectroscopy, in addition to 1H and 13C NMR, they were able to show that a relatively stable intermediate was formed. They proposed that the pseudo-cis isomer, (I), would enable the intermediate to undergo the second part of the reaction sequence, namely ring closure. This reaction sequence was named by van???? or Van der Plas (1978) as the SN(ANRORC) process (addition of the nucleophile, ring opening and ring closure) [scheme 1].
If only two equivalents of hydroxide were used, the intermediate formed from 2-chloro-5-nitropyridine was reasonably stable in the reaction medium. However, over a period of months we observed that the intermediate either slowly isomerized or decomposed to formate. We followed these transformations using 1H NMR spectroscopy. In contrast, 2-chloro-3-nitropyridine in the presence of two equivalents of sodium hydroxide forms a pseudo-cis intermediate that, during work-up, readily isomerizes to a pseudo-trans intermediate, (III). The structures of both of the intermediates from 2-chloro-3-nitropyridine were determined using NMR and X-ray crystallography (Haynes & Pett, 2007).
The dramatic difference between the isomerization rates of intermediates from two very similar starting materials prompted us to continue our investigations with the intermediates from 2-chloro-5-nitropyridine. In order to verify our assumptions concerning the structures of the two intermediates, we conducted crystallization experiments with samples containing predominantly one isomer or the other, as indicated by the 1H NMR spectra.
One sample (as the tetra-n-butylammonium salt) gave disordered monoclinic crystals that were found to consist of a mixture of mainly the pseudo-cis isomer, (I), with a small but significant amount of the pseudo-trans isomer, (II) (Fig. 1a). Several crystals from different crystallization attempts were analyzed, resulting in all cases in similar pseudo-cis to pseudo-trans ratios. For the data set used here, the ratio refined to 91.7 (3) to 8.3 (3)% in favor of the pseudo-cis isomer [scheme 2].
The X-ray crystallographic study using the crystals isolated from a sample that was stable in solution for eight months (again as the tetra-n-butylammonium salt) showed that these crystals were made up only of carbanions in the pseudo-trans geometry, (II) (Fig. 1b). This pure isomer also crystallized with the same monoclinic space group, P21/n, and with an almost identical unit cell volume. The two monoclinic cells have comparable unit cell axes and β angles, but the positions of the glide planes differ. Thus, the designation of the unit cell axes is different; a, b and c in the (I/II) mixed crystal are converted into c, a and b in the crystal of pure (II).
The type of packing in the two different cells is very similar (Fig. 2), with layers of the planar carbanions alternating with the tetra-n-butylammonium cations. The orientation of the ions and their orientation with respect to each other is the same in both cells; only the separation between the ions varies slightly between the two structures. The largest difference is observed for the closest distance of the O atoms of adjacent nitro groups, which is 5.6827 (18) Å in (II) and 5.821 (3) Å in (I/II) [the symmetry operator relating the adjacent molecules is (-x + 1, -y + 1, -z + 1)].
Within the layers, the carbanions are arranged in loosely connected dimers. In both pseudo-trans (II) and disordered (I/II), the nitrile groups are arranged in such a way that the N atom interacts with atom H20 of the neighboring anion to form a very weak intermolecular hydrogen bond (Fig. 3). For the pseudo-cis isomer, (I), the interaction is slightly weaker, with a C20···N3 distance of 3.519 (4) Å. For the pseudo-trans geometry, in both types of crystals, the hydrogen bond is slightly strengthened, and the C···N distances are 3.39 (4) and 3.348 (2) Å in the structures of (I/II) and (II), respectively (see Tables 1 and 2 for the hydrogen-bonding parameters.) However, even this slightly shorter hydrogen bond is not unusually strong. A search of the Cambridge Structural Database for nitrile dimers connected via similar hydrogen bonds revealed 58 compounds with both hydrogen bonds equal to or shorter than 2.8 Å (Version ?; Allen, 2002).
In the pseudo-trans geometry, atom H20 also forms an intramolecular hydrogen bond with the aldehyde atom O3, thus possibly stabilizing the pseudo-trans geometry slightly as compared with the pseudo-cis isomer (Tables 1 and 2, and Fig. 3). Nevertheless, all the hydrogen-bonding interactions seem to be rather weak and are probably not a significant directing force towards the overall packing mode. It seems more likely that the packing is determined by the electrostatic interactions between the alternating layers of carbanions and tetra-n-butylammonium cations.
The C—C bonds in carbanions (I), (II) and (III) are shorter than standard single bonds, indicating considerable delocalization of the negative charge over each anion (Table 3). However, the C19—C20 distances in all three anions are significantly shorter than the other C—C bonds and almost as short as a standard double bond. Also, the C18—N2 distances in the nitro group are shorter than a single C—N bond, while the N2—O1 and N2—O2 distances are longer than an N═O double bond. The bond distances in these three carbanions exhibit a conjugated system of double bonds, revealing that the electron distribution is clearly directed by the nitro group, the most powerful electron withdrawing substituent in the anions. Thus, the structures coincide with what we would expect from the electronegativities of the atoms.