Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106029209/dn3021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106029209/dn3021Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106029209/dn3021IIsup3.hkl |
CCDC references: 621290; 621291
Compound (I) was crystallized from an aqueous solution containing L-proline and picric acid in the stoichiometric ratio of 1:1 at room temperature, by the technique of slow evaporation. Similarly, compound (II) was crystallized from an aqueous solution containing pyridoxine and picric acid in the stoichiometric ratio of 1:1 at room temperature by the technique of slow evaporation. Instead of the expected picric acid complex with pyridoxine, crystals of 2-methylpyridinum picrate were obtained.
All H atoms were placed in geometrically calculated positions and included in the refinement in the riding-model approximation, with N—H = 0.90 Å and C—H = 0.93–0.98 Å in compound (I), and with N—H = 0.86 Å and C—H = 0.93–0.96 Å and in compound (II). In both compounds, Uiso(H) = 1.2–1.5Ueq(C,N). In compound (I), the Cγ atom (C4) of the pyrolidine ring has conformational disorder, with site-occupancy factors of 0.52 (1) and 0.48 (1). In compound (II), one of the O atoms of the picrate anion is disordered, with occupancy factors of 0.71 (1) and 0.29 (1) for atoms O47 and O471. In compound (I), owing to the absence of atoms heavier than Si, the absolute configuration could not be reliably determined and Friedel pairs were merged.
For both compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: ORTEP 3 for Windows (Farrugia, 1997), PLATON (Spek, 2003) and Mercury (Version 1.4.1; Macrae et al., 2006); software used to prepare material for publication: SHELXTL/PC.
C5H10NO2+·C6H2N3O7− | F(000) = 356 |
Mr = 344.25 | Dx = 1.662 Mg m−3 Dm = 1.66 Mg m−3 Dm measured by flotation using a liquid mixture of carbon tetrachloride and bromoform |
MonoclinicP21 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 10.909 (4) Å | θ = 9.9–14.2° |
b = 5.352 (3) Å | µ = 0.15 mm−1 |
c = 12.474 (5) Å | T = 293 K |
β = 109.142 (5)° | Needle, yellow |
V = 688.0 (5) Å3 | 0.3 × 0.2 × 0.12 mm |
Z = 2 |
Nonius MACH3 sealed tube diffractometer | 1590 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.100 |
Graphite monochromator | θmax = 30.0°, θmin = 2.2° |
ω/2θ scans | h = −1→15 |
Absorption correction: ψ scan (North et al., 1968) | k = −6→7 |
Tmin = 0.967, Tmax = 0.981 | l = −17→16 |
3719 measured reflections | 3 standard reflections every 60 min |
2205 independent reflections | intensity decay: none |
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) = 0.169 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1016P)2] where P = (Fo2 + 2Fc2)/3 |
2205 reflections | (Δ/σ)max = 0.001 |
226 parameters | Δρmax = 0.49 e Å−3 |
10 restraints | Δρmin = −0.27 e Å−3 |
C5H10NO2+·C6H2N3O7− | V = 688.0 (5) Å3 |
Mr = 344.25 | Z = 2 |
MonoclinicP21 | Mo Kα radiation |
a = 10.909 (4) Å | µ = 0.15 mm−1 |
b = 5.352 (3) Å | T = 293 K |
c = 12.474 (5) Å | 0.3 × 0.2 × 0.12 mm |
β = 109.142 (5)° |
Nonius MACH3 sealed tube diffractometer | 1590 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.100 |
Tmin = 0.967, Tmax = 0.981 | 3 standard reflections every 60 min |
3719 measured reflections | intensity decay: none |
2205 independent reflections |
R[F2 > 2σ(F2)] = 0.058 | 10 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.49 e Å−3 |
2205 reflections | Δρmin = −0.27 e Å−3 |
226 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) | |
O1A | 0.5965 (3) | 0.4460 (5) | 0.9635 (2) | 0.0504 (7) | |
O1B | 0.4482 (2) | 0.2628 (5) | 0.8176 (2) | 0.0441 (6) | |
H1B | 0.4118 | 0.3986 | 0.8119 | 0.066* | |
C1 | 0.5557 (3) | 0.2674 (6) | 0.9041 (3) | 0.0305 (6) | |
C2 | 0.6275 (3) | 0.0212 (6) | 0.9191 (3) | 0.0342 (6) | |
H2 | 0.5666 | −0.1190 | 0.9064 | 0.041* | |
C3 | 0.7083 (3) | 0.0030 (10) | 0.8391 (3) | 0.0474 (9) | 0.52 |
H3A | 0.6755 | −0.1281 | 0.7834 | 0.057* | 0.52 |
H3B | 0.7069 | 0.1599 | 0.7999 | 0.057* | 0.52 |
C4 | 0.8447 (7) | −0.0576 (19) | 0.9166 (7) | 0.0455 (17) | 0.52 |
H4A | 0.8584 | −0.2370 | 0.9212 | 0.055* | 0.52 |
H4B | 0.9086 | 0.0178 | 0.8878 | 0.055* | 0.52 |
C5 | 0.8560 (3) | 0.0392 (18) | 1.0229 (4) | 0.0767 (19) | 0.52 |
H5A | 0.8803 | 0.2142 | 1.0275 | 0.092* | 0.52 |
H5B | 0.9211 | −0.0516 | 1.0821 | 0.092* | 0.52 |
N1 | 0.7249 (3) | 0.0087 (7) | 1.0354 (2) | 0.0439 (7) | |
H1A | 0.7196 | −0.1393 | 1.0679 | 0.053* | |
H1C | 0.7104 | 0.1312 | 1.0792 | 0.053* | |
C31 | 0.7083 (3) | 0.0030 (10) | 0.8391 (3) | 0.0474 (9) | 0.48 |
H3C | 0.7141 | −0.1683 | 0.8158 | 0.057* | 0.48 |
H3D | 0.6718 | 0.1059 | 0.7722 | 0.057* | 0.48 |
C41 | 0.8392 (7) | 0.100 (2) | 0.9115 (7) | 0.052 (2) | 0.48 |
H41A | 0.9072 | 0.0239 | 0.8881 | 0.062* | 0.48 |
H41B | 0.8433 | 0.2793 | 0.9033 | 0.062* | 0.48 |
C51 | 0.8560 (3) | 0.0392 (18) | 1.0229 (4) | 0.0767 (19) | 0.48 |
H5C | 0.9037 | 0.1707 | 1.0728 | 0.092* | 0.48 |
H5D | 0.9049 | −0.1149 | 1.0433 | 0.092* | 0.48 |
O11 | 0.3453 (2) | 0.6864 (5) | 0.76837 (19) | 0.0387 (6) | |
O12 | 0.5313 (2) | 0.5462 (7) | 0.6679 (2) | 0.0537 (8) | |
O13 | 0.4166 (3) | 0.3670 (6) | 0.5124 (3) | 0.0625 (8) | |
O14 | 0.1507 (3) | 1.0047 (9) | 0.2598 (2) | 0.0617 (9) | |
O15 | 0.0693 (3) | 1.3017 (9) | 0.3313 (3) | 0.0742 (11) | |
O16 | 0.1150 (3) | 1.3073 (6) | 0.7175 (3) | 0.0636 (9) | |
O17 | 0.1876 (3) | 0.9980 (7) | 0.8269 (2) | 0.0541 (8) | |
N11 | 0.4326 (2) | 0.5253 (6) | 0.5860 (3) | 0.0380 (6) | |
N12 | 0.1304 (3) | 1.1055 (7) | 0.3397 (3) | 0.0453 (8) | |
N13 | 0.1659 (2) | 1.0970 (6) | 0.7365 (3) | 0.0393 (7) | |
C11 | 0.2968 (3) | 0.7829 (6) | 0.6720 (3) | 0.0287 (6) | |
C12 | 0.3281 (3) | 0.7069 (6) | 0.5727 (3) | 0.0318 (6) | |
C13 | 0.2725 (3) | 0.8005 (7) | 0.4665 (3) | 0.0347 (7) | |
H13 | 0.2942 | 0.7374 | 0.4056 | 0.042* | |
C14 | 0.1825 (3) | 0.9922 (7) | 0.4508 (3) | 0.0351 (7) | |
C15 | 0.1499 (3) | 1.0857 (7) | 0.5400 (3) | 0.0359 (7) | |
H15 | 0.0919 | 1.2183 | 0.5289 | 0.043* | |
C16 | 0.2034 (3) | 0.9823 (6) | 0.6460 (3) | 0.0308 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0620 (15) | 0.0286 (12) | 0.0459 (13) | 0.0129 (12) | −0.0022 (12) | −0.0044 (11) |
O1B | 0.0359 (11) | 0.0293 (12) | 0.0579 (15) | 0.0028 (11) | 0.0031 (10) | 0.0071 (12) |
C1 | 0.0372 (14) | 0.0221 (13) | 0.0344 (14) | 0.0042 (13) | 0.0147 (12) | 0.0055 (12) |
C2 | 0.0341 (13) | 0.0204 (12) | 0.0504 (17) | 0.0022 (12) | 0.0167 (13) | 0.0045 (14) |
C3 | 0.0468 (17) | 0.056 (2) | 0.0407 (17) | 0.009 (2) | 0.0160 (14) | −0.0078 (19) |
C4 | 0.040 (4) | 0.040 (4) | 0.059 (5) | 0.010 (3) | 0.019 (3) | −0.001 (4) |
C5 | 0.0315 (15) | 0.142 (6) | 0.056 (2) | 0.013 (3) | 0.0129 (16) | 0.005 (4) |
N1 | 0.0476 (14) | 0.0489 (18) | 0.0407 (14) | 0.0229 (16) | 0.0222 (12) | 0.0195 (15) |
C31 | 0.0468 (17) | 0.056 (2) | 0.0407 (17) | 0.009 (2) | 0.0160 (14) | −0.0078 (19) |
C41 | 0.045 (4) | 0.056 (6) | 0.065 (6) | 0.003 (5) | 0.032 (4) | 0.008 (5) |
C51 | 0.0315 (15) | 0.142 (6) | 0.056 (2) | 0.013 (3) | 0.0129 (16) | 0.005 (4) |
O11 | 0.0398 (12) | 0.0346 (11) | 0.0396 (12) | 0.0117 (11) | 0.0100 (10) | 0.0064 (11) |
O12 | 0.0369 (12) | 0.065 (2) | 0.0578 (15) | 0.0196 (14) | 0.0135 (11) | 0.0124 (16) |
O13 | 0.0572 (16) | 0.0412 (14) | 0.096 (2) | 0.0011 (14) | 0.0345 (16) | −0.0226 (17) |
O14 | 0.0555 (15) | 0.087 (2) | 0.0412 (13) | 0.0027 (19) | 0.0142 (12) | 0.0135 (19) |
O15 | 0.0712 (19) | 0.072 (2) | 0.074 (2) | 0.033 (2) | 0.0164 (17) | 0.035 (2) |
O16 | 0.0754 (19) | 0.0422 (15) | 0.073 (2) | 0.0232 (16) | 0.0235 (17) | −0.0087 (16) |
O17 | 0.0542 (14) | 0.069 (2) | 0.0382 (13) | 0.0208 (17) | 0.0136 (11) | −0.0008 (15) |
N11 | 0.0349 (12) | 0.0294 (13) | 0.0545 (16) | 0.0061 (12) | 0.0212 (12) | 0.0087 (14) |
N12 | 0.0335 (13) | 0.0557 (19) | 0.0420 (15) | 0.0024 (15) | 0.0059 (12) | 0.0167 (16) |
N13 | 0.0283 (11) | 0.0399 (15) | 0.0445 (16) | 0.0039 (12) | 0.0049 (11) | −0.0137 (14) |
C11 | 0.0223 (11) | 0.0239 (12) | 0.0367 (15) | −0.0014 (11) | 0.0052 (11) | −0.0016 (13) |
C12 | 0.0254 (12) | 0.0252 (13) | 0.0435 (16) | 0.0015 (11) | 0.0094 (12) | 0.0009 (14) |
C13 | 0.0313 (13) | 0.0302 (15) | 0.0441 (17) | −0.0006 (14) | 0.0143 (12) | −0.0007 (15) |
C14 | 0.0285 (12) | 0.0366 (16) | 0.0368 (14) | −0.0015 (14) | 0.0061 (11) | 0.0077 (15) |
C15 | 0.0238 (12) | 0.0307 (15) | 0.0467 (17) | 0.0018 (12) | 0.0027 (12) | 0.0051 (14) |
C16 | 0.0253 (12) | 0.0283 (14) | 0.0362 (14) | −0.0004 (12) | 0.0065 (11) | −0.0054 (13) |
O1A—C1 | 1.202 (4) | C41—H41B | 0.9700 |
O1B—C1 | 1.308 (4) | O11—C11 | 1.255 (4) |
O1B—H1B | 0.8200 | O12—N11 | 1.222 (4) |
C1—C2 | 1.513 (4) | O13—N11 | 1.219 (4) |
C2—N1 | 1.493 (4) | O14—N12 | 1.215 (5) |
C2—C3 | 1.535 (5) | O15—N12 | 1.229 (5) |
C2—H2 | 0.9800 | O16—N13 | 1.243 (4) |
C3—C4 | 1.520 (8) | O17—N13 | 1.197 (4) |
C3—H3A | 0.9700 | N11—C12 | 1.466 (4) |
C3—H3B | 0.9700 | N12—C14 | 1.448 (4) |
C4—C5 | 1.392 (9) | N13—C16 | 1.456 (4) |
C4—H4A | 0.9700 | C11—C16 | 1.438 (4) |
C4—H4B | 0.9700 | C11—C12 | 1.447 (4) |
C5—N1 | 1.497 (5) | C12—C13 | 1.359 (5) |
C5—H5A | 0.9700 | C13—C14 | 1.388 (5) |
C5—H5B | 0.9700 | C13—H13 | 0.9300 |
N1—H1A | 0.9000 | C14—C15 | 1.370 (5) |
N1—H1C | 0.9000 | C15—C16 | 1.375 (4) |
C41—H41A | 0.9700 | C15—H15 | 0.9300 |
C1—O1B—H1B | 109.5 | C2—N1—H1C | 110.3 |
O1A—C1—O1B | 125.0 (3) | C5—N1—H1C | 110.3 |
O1A—C1—C2 | 123.0 (3) | H1A—N1—H1C | 108.6 |
O1B—C1—C2 | 111.9 (3) | H41A—C41—H41B | 108.4 |
N1—C2—C1 | 109.5 (3) | O13—N11—O12 | 124.2 (3) |
N1—C2—C3 | 104.6 (2) | O13—N11—C12 | 117.5 (3) |
C1—C2—C3 | 111.1 (3) | O12—N11—C12 | 118.3 (3) |
N1—C2—H2 | 110.5 | O14—N12—O15 | 123.3 (4) |
C1—C2—H2 | 110.5 | O14—N12—C14 | 118.6 (3) |
C3—C2—H2 | 110.5 | O15—N12—C14 | 118.1 (4) |
C4—C3—C2 | 104.6 (4) | O17—N13—O16 | 121.2 (3) |
C4—C3—H3A | 110.8 | O17—N13—C16 | 121.6 (3) |
C2—C3—H3A | 110.8 | O16—N13—C16 | 117.0 (3) |
C4—C3—H3B | 110.8 | O11—C11—C16 | 124.5 (3) |
C2—C3—H3B | 110.8 | O11—C11—C12 | 124.1 (3) |
H3A—C3—H3B | 108.9 | C16—C11—C12 | 111.4 (2) |
C5—C4—C3 | 106.8 (5) | C13—C12—C11 | 125.2 (3) |
C5—C4—H4A | 110.4 | C13—C12—N11 | 115.9 (3) |
C3—C4—H4A | 110.4 | C11—C12—N11 | 118.9 (3) |
C5—C4—H4B | 110.4 | C12—C13—C14 | 118.6 (3) |
C3—C4—H4B | 110.4 | C12—C13—H13 | 120.7 |
H4A—C4—H4B | 108.6 | C14—C13—H13 | 120.7 |
C4—C5—N1 | 105.6 (5) | C15—C14—C13 | 121.0 (3) |
C4—C5—H5A | 110.6 | C15—C14—N12 | 120.0 (3) |
N1—C5—H5A | 110.6 | C13—C14—N12 | 118.8 (3) |
C4—C5—H5B | 110.6 | C14—C15—C16 | 119.5 (3) |
N1—C5—H5B | 110.6 | C14—C15—H15 | 120.2 |
H5A—C5—H5B | 108.7 | C16—C15—H15 | 120.2 |
C2—N1—C5 | 107.1 (3) | C15—C16—C11 | 124.1 (3) |
C2—N1—H1A | 110.3 | C15—C16—N13 | 115.9 (3) |
C5—N1—H1A | 110.3 | C11—C16—N13 | 119.8 (3) |
O1A—C1—C2—N1 | 19.1 (5) | N11—C12—C13—C14 | −173.3 (3) |
O1B—C1—C2—N1 | −163.0 (3) | C12—C13—C14—C15 | −0.1 (5) |
O1A—C1—C2—C3 | −95.9 (4) | C12—C13—C14—N12 | 175.3 (3) |
O1B—C1—C2—C3 | 82.0 (3) | O14—N12—C14—C15 | −173.0 (3) |
N1—C2—C3—C4 | 8.2 (6) | O15—N12—C14—C15 | 8.1 (5) |
C1—C2—C3—C4 | 126.2 (5) | O14—N12—C14—C13 | 11.5 (5) |
C2—C3—C4—C5 | −27.1 (8) | O15—N12—C14—C13 | −167.4 (3) |
C3—C4—C5—N1 | 34.7 (9) | C13—C14—C15—C16 | −2.4 (5) |
C1—C2—N1—C5 | −107.3 (5) | N12—C14—C15—C16 | −177.8 (3) |
C3—C2—N1—C5 | 11.8 (5) | C14—C15—C16—C11 | 2.1 (5) |
C4—C5—N1—C2 | −29.5 (8) | C14—C15—C16—N13 | 178.5 (3) |
O11—C11—C12—C13 | 176.8 (3) | O11—C11—C16—C15 | −179.5 (3) |
C16—C11—C12—C13 | −3.2 (4) | C12—C11—C16—C15 | 0.6 (4) |
O11—C11—C12—N11 | −6.9 (5) | O11—C11—C16—N13 | 4.2 (5) |
C16—C11—C12—N11 | 173.1 (3) | C12—C11—C16—N13 | −175.8 (3) |
O13—N11—C12—C13 | −42.6 (4) | O17—N13—C16—C15 | 166.8 (3) |
O12—N11—C12—C13 | 135.4 (3) | O16—N13—C16—C15 | −16.1 (4) |
O13—N11—C12—C11 | 140.7 (3) | O17—N13—C16—C11 | −16.6 (5) |
O12—N11—C12—C11 | −41.3 (4) | O16—N13—C16—C11 | 160.5 (3) |
C11—C12—C13—C14 | 3.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H1B···O11 | 0.82 | 1.71 | 2.515 (4) | 165 |
N1—H1C···O11i | 0.90 | 2.20 | 2.952 (4) | 141 |
N1—H1A···O17ii | 0.90 | 2.38 | 3.202 (5) | 153 |
N1—H1C···O17i | 0.90 | 2.37 | 3.106 (5) | 139 |
Symmetry codes: (i) −x+1, y−1/2, −z+2; (ii) −x+1, y−3/2, −z+2. |
C6H8N+·C6H2N3O7− | Z = 4 |
Mr = 322.24 | F(000) = 664 |
TriclinicP1 | Dx = 1.575 Mg m−3 Dm = 1.57 Mg m−3 Dm measured by flotation using a liquid mixture of xylene and carbon tetrachloride |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.211 (3) Å | Cell parameters from 25 reflections |
b = 11.806 (4) Å | θ = 10.5–14.0° |
c = 14.388 (4) Å | µ = 0.13 mm−1 |
α = 85.428 (5)° | T = 293 K |
β = 82.863 (5)° | Block, yellow |
γ = 79.726 (4)° | 0.25 × 0.2 × 0.15 mm |
V = 1359.4 (8) Å3 |
Nonius MACH3 sealed tube diffractometer | 3255 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω/2θ scans | h = −1→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −13→14 |
Tmin = 0.970, Tmax = 0.980 | l = −17→17 |
5848 measured reflections | 3 standard reflections every 60 min |
4762 independent reflections | intensity decay: none |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.5564P] where P = (Fo2 + 2Fc2)/3 |
4762 reflections | (Δ/σ)max < 0.001 |
426 parameters | Δρmax = 0.32 e Å−3 |
3 restraints | Δρmin = −0.27 e Å−3 |
C6H8N+·C6H2N3O7− | γ = 79.726 (4)° |
Mr = 322.24 | V = 1359.4 (8) Å3 |
TriclinicP1 | Z = 4 |
a = 8.211 (3) Å | Mo Kα radiation |
b = 11.806 (4) Å | µ = 0.13 mm−1 |
c = 14.388 (4) Å | T = 293 K |
α = 85.428 (5)° | 0.25 × 0.2 × 0.15 mm |
β = 82.863 (5)° |
Nonius MACH3 sealed tube diffractometer | 3255 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.015 |
Tmin = 0.970, Tmax = 0.980 | 3 standard reflections every 60 min |
5848 measured reflections | intensity decay: none |
4762 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 3 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.32 e Å−3 |
4762 reflections | Δρmin = −0.27 e Å−3 |
426 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) | |
N11 | 0.0555 (2) | 0.16222 (16) | 0.47838 (15) | 0.0456 (5) | |
H11 | −0.0174 | 0.2122 | 0.4526 | 0.055* | |
C12 | 0.0662 (3) | 0.1673 (2) | 0.5690 (2) | 0.0525 (6) | |
H12 | −0.0034 | 0.2248 | 0.6024 | 0.063* | |
C13 | 0.1770 (4) | 0.0900 (2) | 0.6135 (2) | 0.0617 (7) | |
H13 | 0.1856 | 0.0944 | 0.6769 | 0.074* | |
C14 | 0.2757 (4) | 0.0056 (2) | 0.5634 (3) | 0.0673 (8) | |
H14 | 0.3510 | −0.0496 | 0.5929 | 0.081* | |
C15 | 0.2646 (3) | 0.0018 (2) | 0.4707 (2) | 0.0637 (8) | |
H15 | 0.3327 | −0.0561 | 0.4370 | 0.076* | |
C16 | 0.1523 (3) | 0.0835 (2) | 0.42510 (19) | 0.0495 (6) | |
C17 | 0.1331 (5) | 0.0904 (3) | 0.3243 (2) | 0.0834 (10) | |
H17A | 0.0179 | 0.1151 | 0.3156 | 0.125* | |
H17B | 0.1713 | 0.0159 | 0.2997 | 0.125* | |
H17C | 0.1977 | 0.1447 | 0.2919 | 0.125* | |
N21 | 0.5579 (2) | 0.15320 (15) | 0.02808 (15) | 0.0448 (5) | |
H21 | 0.4770 | 0.1973 | 0.0580 | 0.054* | |
C22 | 0.5970 (3) | 0.1786 (2) | −0.06285 (19) | 0.0509 (6) | |
H22 | 0.5380 | 0.2436 | −0.0919 | 0.061* | |
C23 | 0.7219 (3) | 0.1108 (2) | −0.1136 (2) | 0.0557 (7) | |
H23 | 0.7509 | 0.1289 | −0.1769 | 0.067* | |
C24 | 0.8044 (3) | 0.0144 (2) | −0.0686 (2) | 0.0601 (7) | |
H24 | 0.8885 | −0.0348 | −0.1020 | 0.072* | |
C25 | 0.7638 (3) | −0.0094 (2) | 0.0244 (2) | 0.0551 (7) | |
H25 | 0.8208 | −0.0745 | 0.0542 | 0.066* | |
C26 | 0.6387 (3) | 0.06220 (19) | 0.07506 (18) | 0.0451 (6) | |
C27 | 0.5891 (4) | 0.0470 (3) | 0.1772 (2) | 0.0691 (8) | |
H27A | 0.6613 | 0.0801 | 0.2107 | 0.104* | |
H27B | 0.5977 | −0.0337 | 0.1952 | 0.104* | |
H27C | 0.4762 | 0.0848 | 0.1918 | 0.104* | |
O31 | 0.26158 (19) | 0.26093 (13) | 0.10363 (13) | 0.0509 (4) | |
O32 | −0.0606 (3) | 0.24090 (17) | 0.03931 (16) | 0.0750 (6) | |
O33 | −0.1624 (4) | 0.2549 (2) | 0.18142 (17) | 0.1059 (9) | |
O34 | −0.2623 (2) | 0.70981 (16) | 0.14801 (16) | 0.0689 (6) | |
O35 | −0.0467 (2) | 0.77191 (15) | 0.18087 (14) | 0.0626 (5) | |
O36 | 0.4826 (2) | 0.53746 (15) | 0.14666 (14) | 0.0609 (5) | |
O37 | 0.5224 (2) | 0.38072 (16) | 0.07610 (17) | 0.0736 (6) | |
N31 | −0.0786 (2) | 0.28612 (17) | 0.11263 (17) | 0.0482 (5) | |
N32 | −0.1139 (3) | 0.69502 (17) | 0.15822 (15) | 0.0472 (5) | |
N33 | 0.4295 (2) | 0.45950 (17) | 0.11523 (14) | 0.0448 (5) | |
C31 | 0.1830 (3) | 0.36127 (18) | 0.11291 (16) | 0.0385 (5) | |
C32 | 0.0035 (3) | 0.38540 (18) | 0.11985 (16) | 0.0378 (5) | |
C33 | −0.0943 (3) | 0.48951 (19) | 0.13400 (16) | 0.0407 (5) | |
H33 | −0.2097 | 0.4983 | 0.1373 | 0.049* | |
C34 | −0.0160 (3) | 0.58273 (18) | 0.14340 (16) | 0.0400 (5) | |
C35 | 0.1546 (3) | 0.56928 (19) | 0.13908 (16) | 0.0400 (5) | |
H35 | 0.2047 | 0.6319 | 0.1473 | 0.048* | |
C36 | 0.2512 (3) | 0.46385 (18) | 0.12263 (16) | 0.0376 (5) | |
O41 | −0.2188 (2) | 0.28144 (13) | 0.41520 (13) | 0.0549 (5) | |
O42 | −0.6001 (4) | 0.2878 (2) | 0.31333 (18) | 0.1024 (9) | |
O43 | −0.5605 (3) | 0.24710 (17) | 0.45615 (17) | 0.0802 (7) | |
O44 | −0.7095 (2) | 0.72988 (16) | 0.32174 (16) | 0.0715 (6) | |
O45 | −0.4888 (2) | 0.80333 (14) | 0.32766 (14) | 0.0625 (5) | |
O46 | 0.0213 (2) | 0.56425 (17) | 0.3695 (2) | 0.0883 (8) | |
O47 | 0.0416 (6) | 0.3939 (4) | 0.4240 (3) | 0.0793 (14) | 0.71 |
O471 | 0.0475 (12) | 0.3818 (8) | 0.3708 (6) | 0.058 (2) | 0.29 |
N41 | −0.5474 (2) | 0.30597 (17) | 0.38478 (17) | 0.0500 (5) | |
N42 | −0.5624 (3) | 0.72029 (17) | 0.33411 (15) | 0.0487 (5) | |
N43 | −0.0402 (2) | 0.47909 (17) | 0.38919 (15) | 0.0499 (5) | |
C41 | −0.2903 (3) | 0.38214 (18) | 0.39647 (16) | 0.0384 (5) | |
C42 | −0.4640 (3) | 0.40615 (18) | 0.38166 (16) | 0.0377 (5) | |
C43 | −0.5534 (3) | 0.51179 (19) | 0.36168 (16) | 0.0405 (5) | |
H43 | −0.6651 | 0.5206 | 0.3522 | 0.049* | |
C44 | −0.4718 (3) | 0.60678 (18) | 0.35587 (16) | 0.0398 (5) | |
C45 | −0.3061 (3) | 0.59369 (18) | 0.36621 (16) | 0.0405 (5) | |
H45 | −0.2537 | 0.6579 | 0.3608 | 0.049* | |
C46 | −0.2166 (3) | 0.48558 (18) | 0.38464 (16) | 0.0389 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.0345 (11) | 0.0340 (10) | 0.0670 (14) | −0.0017 (8) | −0.0094 (9) | 0.0011 (9) |
C12 | 0.0461 (15) | 0.0418 (14) | 0.0685 (18) | −0.0048 (12) | −0.0005 (12) | −0.0117 (12) |
C13 | 0.0624 (18) | 0.0546 (16) | 0.0719 (19) | −0.0135 (14) | −0.0211 (15) | 0.0028 (14) |
C14 | 0.0538 (17) | 0.0448 (15) | 0.103 (3) | −0.0008 (13) | −0.0277 (17) | 0.0061 (16) |
C15 | 0.0442 (16) | 0.0369 (14) | 0.106 (3) | 0.0022 (12) | 0.0056 (15) | −0.0197 (14) |
C16 | 0.0427 (14) | 0.0407 (13) | 0.0663 (17) | −0.0139 (11) | 0.0033 (12) | −0.0096 (12) |
C17 | 0.094 (3) | 0.093 (2) | 0.071 (2) | −0.040 (2) | 0.0044 (18) | −0.0146 (17) |
N21 | 0.0339 (10) | 0.0341 (10) | 0.0650 (14) | −0.0004 (8) | −0.0059 (9) | −0.0066 (9) |
C22 | 0.0486 (15) | 0.0397 (13) | 0.0650 (17) | −0.0039 (11) | −0.0191 (13) | 0.0042 (12) |
C23 | 0.0591 (17) | 0.0494 (15) | 0.0593 (16) | −0.0105 (13) | −0.0052 (13) | −0.0071 (12) |
C24 | 0.0523 (16) | 0.0470 (15) | 0.078 (2) | −0.0003 (13) | 0.0013 (14) | −0.0159 (14) |
C25 | 0.0461 (15) | 0.0324 (12) | 0.085 (2) | 0.0053 (11) | −0.0183 (14) | −0.0011 (12) |
C26 | 0.0399 (13) | 0.0343 (12) | 0.0631 (16) | −0.0085 (10) | −0.0114 (11) | −0.0006 (11) |
C27 | 0.075 (2) | 0.0675 (19) | 0.0670 (19) | −0.0209 (16) | −0.0092 (15) | 0.0049 (14) |
O31 | 0.0355 (9) | 0.0335 (9) | 0.0811 (12) | 0.0008 (7) | −0.0040 (8) | −0.0073 (8) |
O32 | 0.0802 (15) | 0.0612 (12) | 0.0909 (15) | −0.0254 (11) | −0.0022 (12) | −0.0310 (11) |
O33 | 0.137 (2) | 0.122 (2) | 0.0800 (16) | −0.095 (2) | −0.0008 (15) | 0.0086 (14) |
O34 | 0.0368 (11) | 0.0501 (11) | 0.1154 (17) | 0.0070 (8) | −0.0119 (10) | −0.0058 (10) |
O35 | 0.0562 (11) | 0.0395 (10) | 0.0928 (14) | −0.0023 (9) | −0.0109 (10) | −0.0184 (9) |
O36 | 0.0381 (10) | 0.0553 (11) | 0.0949 (15) | −0.0128 (8) | −0.0143 (9) | −0.0178 (10) |
O37 | 0.0334 (10) | 0.0583 (12) | 0.1290 (18) | −0.0033 (9) | 0.0053 (10) | −0.0371 (12) |
N31 | 0.0386 (11) | 0.0417 (11) | 0.0666 (14) | −0.0105 (9) | −0.0124 (10) | 0.0012 (11) |
N32 | 0.0384 (12) | 0.0376 (11) | 0.0624 (13) | 0.0008 (9) | −0.0031 (9) | −0.0038 (9) |
N33 | 0.0308 (10) | 0.0424 (11) | 0.0617 (13) | −0.0056 (9) | −0.0055 (9) | −0.0060 (9) |
C31 | 0.0334 (12) | 0.0357 (12) | 0.0455 (13) | −0.0034 (10) | −0.0044 (10) | −0.0024 (9) |
C32 | 0.0325 (12) | 0.0347 (12) | 0.0475 (13) | −0.0082 (9) | −0.0069 (10) | −0.0013 (9) |
C33 | 0.0277 (12) | 0.0422 (13) | 0.0512 (14) | −0.0035 (10) | −0.0052 (10) | −0.0007 (10) |
C34 | 0.0341 (12) | 0.0328 (11) | 0.0511 (14) | 0.0002 (9) | −0.0049 (10) | −0.0040 (10) |
C35 | 0.0341 (12) | 0.0350 (12) | 0.0521 (14) | −0.0070 (9) | −0.0068 (10) | −0.0044 (10) |
C36 | 0.0262 (11) | 0.0390 (12) | 0.0479 (13) | −0.0039 (9) | −0.0066 (9) | −0.0036 (10) |
O41 | 0.0421 (10) | 0.0350 (9) | 0.0875 (13) | −0.0010 (7) | −0.0201 (9) | 0.0048 (8) |
O42 | 0.131 (2) | 0.1091 (19) | 0.0918 (17) | −0.0722 (18) | −0.0236 (16) | −0.0221 (14) |
O43 | 0.0923 (16) | 0.0548 (12) | 0.1009 (17) | −0.0361 (12) | −0.0225 (13) | 0.0215 (12) |
O44 | 0.0405 (11) | 0.0528 (11) | 0.1144 (17) | 0.0066 (9) | −0.0142 (11) | 0.0127 (11) |
O45 | 0.0605 (12) | 0.0321 (9) | 0.0925 (14) | −0.0063 (9) | −0.0060 (10) | 0.0043 (9) |
O46 | 0.0420 (11) | 0.0525 (12) | 0.174 (2) | −0.0187 (10) | −0.0195 (13) | 0.0079 (13) |
O47 | 0.050 (2) | 0.053 (2) | 0.141 (4) | −0.0125 (16) | −0.048 (3) | 0.027 (3) |
O471 | 0.031 (4) | 0.055 (5) | 0.085 (6) | 0.000 (3) | −0.013 (5) | 0.001 (5) |
N41 | 0.0405 (12) | 0.0391 (11) | 0.0729 (15) | −0.0104 (9) | −0.0080 (11) | −0.0080 (11) |
N42 | 0.0432 (12) | 0.0367 (11) | 0.0616 (13) | 0.0016 (9) | −0.0028 (10) | 0.0020 (9) |
N43 | 0.0359 (11) | 0.0437 (12) | 0.0700 (14) | −0.0073 (10) | −0.0100 (10) | 0.0044 (10) |
C41 | 0.0365 (12) | 0.0336 (12) | 0.0448 (13) | −0.0034 (10) | −0.0066 (10) | −0.0023 (9) |
C42 | 0.0354 (12) | 0.0312 (11) | 0.0476 (13) | −0.0082 (9) | −0.0050 (10) | −0.0027 (9) |
C43 | 0.0313 (12) | 0.0401 (12) | 0.0494 (14) | −0.0031 (10) | −0.0065 (10) | −0.0029 (10) |
C44 | 0.0376 (13) | 0.0316 (11) | 0.0479 (13) | −0.0009 (10) | −0.0046 (10) | 0.0002 (9) |
C45 | 0.0380 (13) | 0.0337 (12) | 0.0498 (14) | −0.0086 (10) | −0.0034 (10) | −0.0003 (10) |
C46 | 0.0299 (11) | 0.0386 (12) | 0.0478 (13) | −0.0053 (10) | −0.0059 (10) | 0.0005 (10) |
N11—C12 | 1.324 (3) | O35—N32 | 1.227 (3) |
N11—C16 | 1.335 (3) | O36—N33 | 1.225 (2) |
N11—H11 | 0.8600 | O37—N33 | 1.219 (2) |
C12—C13 | 1.350 (4) | N31—C32 | 1.469 (3) |
C12—H12 | 0.9300 | N32—C34 | 1.439 (3) |
C13—C14 | 1.361 (4) | N33—C36 | 1.447 (3) |
C13—H13 | 0.9300 | C31—C32 | 1.442 (3) |
C14—C15 | 1.353 (4) | C31—C36 | 1.445 (3) |
C14—H14 | 0.9300 | C32—C33 | 1.358 (3) |
C15—C16 | 1.394 (4) | C33—C34 | 1.393 (3) |
C15—H15 | 0.9300 | C33—H33 | 0.9300 |
C16—C17 | 1.472 (4) | C34—C35 | 1.376 (3) |
C17—H17A | 0.9600 | C35—C36 | 1.372 (3) |
C17—H17B | 0.9600 | C35—H35 | 0.9300 |
C17—H17C | 0.9600 | O41—C41 | 1.253 (3) |
N21—C22 | 1.331 (3) | O42—N41 | 1.212 (3) |
N21—C26 | 1.339 (3) | O43—N41 | 1.198 (3) |
N21—H21 | 0.8600 | O44—N42 | 1.227 (3) |
C22—C23 | 1.357 (4) | O45—N42 | 1.232 (3) |
C22—H22 | 0.9300 | O46—N43 | 1.202 (3) |
C23—C24 | 1.374 (4) | O47—O471 | 0.784 (8) |
C23—H23 | 0.9300 | O47—N43 | 1.214 (4) |
C24—C25 | 1.357 (4) | O471—N43 | 1.271 (9) |
C24—H24 | 0.9300 | N41—C42 | 1.463 (3) |
C25—C26 | 1.379 (4) | N42—C44 | 1.443 (3) |
C25—H25 | 0.9300 | N43—C46 | 1.447 (3) |
C26—C27 | 1.480 (4) | C41—C42 | 1.443 (3) |
C27—H27A | 0.9600 | C41—C46 | 1.446 (3) |
C27—H27B | 0.9600 | C42—C43 | 1.359 (3) |
C27—H27C | 0.9600 | C43—C44 | 1.398 (3) |
O31—C31 | 1.252 (3) | C43—H43 | 0.9300 |
O32—N31 | 1.201 (3) | C44—C45 | 1.367 (3) |
O33—N31 | 1.205 (3) | C45—C46 | 1.378 (3) |
O34—N32 | 1.226 (3) | C45—H45 | 0.9300 |
C12—N11—C16 | 123.3 (2) | O37—N33—O36 | 121.85 (19) |
C12—N11—H11 | 118.3 | O37—N33—C36 | 119.61 (19) |
C16—N11—H11 | 118.3 | O36—N33—C36 | 118.51 (19) |
N11—C12—C13 | 120.9 (2) | O31—C31—C32 | 121.3 (2) |
N11—C12—H12 | 119.6 | O31—C31—C36 | 127.2 (2) |
C13—C12—H12 | 119.6 | C32—C31—C36 | 111.43 (19) |
C12—C13—C14 | 118.5 (3) | C33—C32—C31 | 126.2 (2) |
C12—C13—H13 | 120.7 | C33—C32—N31 | 118.0 (2) |
C14—C13—H13 | 120.7 | C31—C32—N31 | 115.80 (19) |
C15—C14—C13 | 120.1 (3) | C32—C33—C34 | 117.7 (2) |
C15—C14—H14 | 120.0 | C32—C33—H33 | 121.1 |
C13—C14—H14 | 120.0 | C34—C33—H33 | 121.1 |
C14—C15—C16 | 120.9 (2) | C35—C34—C33 | 121.0 (2) |
C14—C15—H15 | 119.6 | C35—C34—N32 | 119.0 (2) |
C16—C15—H15 | 119.6 | C33—C34—N32 | 120.0 (2) |
N11—C16—C15 | 116.3 (2) | C36—C35—C34 | 120.3 (2) |
N11—C16—C17 | 118.0 (3) | C36—C35—H35 | 119.9 |
C15—C16—C17 | 125.7 (3) | C34—C35—H35 | 119.9 |
C16—C17—H17A | 109.5 | C35—C36—C31 | 123.3 (2) |
C16—C17—H17B | 109.5 | C35—C36—N33 | 116.17 (19) |
H17A—C17—H17B | 109.5 | C31—C36—N33 | 120.50 (19) |
C16—C17—H17C | 109.5 | O471—O47—N43 | 75.6 (8) |
H17A—C17—H17C | 109.5 | O47—O471—N43 | 67.7 (8) |
H17B—C17—H17C | 109.5 | O43—N41—O42 | 123.7 (2) |
C22—N21—C26 | 123.1 (2) | O43—N41—C42 | 119.5 (2) |
C22—N21—H21 | 118.5 | O42—N41—C42 | 116.9 (2) |
C26—N21—H21 | 118.5 | O44—N42—O45 | 122.7 (2) |
N21—C22—C23 | 120.8 (2) | O44—N42—C44 | 118.5 (2) |
N21—C22—H22 | 119.6 | O45—N42—C44 | 118.9 (2) |
C23—C22—H22 | 119.6 | O46—N43—O47 | 119.3 (3) |
C22—C23—C24 | 117.9 (3) | O46—N43—O471 | 118.5 (5) |
C22—C23—H23 | 121.0 | O47—N43—O471 | 36.7 (4) |
C24—C23—H23 | 121.0 | O46—N43—C46 | 119.2 (2) |
C25—C24—C23 | 120.4 (2) | O47—N43—C46 | 120.9 (3) |
C25—C24—H24 | 119.8 | O471—N43—C46 | 114.5 (5) |
C23—C24—H24 | 119.8 | O41—C41—C42 | 121.2 (2) |
C24—C25—C26 | 120.7 (2) | O41—C41—C46 | 127.1 (2) |
C24—C25—H25 | 119.7 | C42—C41—C46 | 111.68 (18) |
C26—C25—H25 | 119.7 | C43—C42—C41 | 125.9 (2) |
N21—C26—C25 | 117.1 (2) | C43—C42—N41 | 117.9 (2) |
N21—C26—C27 | 117.8 (2) | C41—C42—N41 | 116.10 (19) |
C25—C26—C27 | 125.1 (2) | C42—C43—C44 | 117.7 (2) |
C26—C27—H27A | 109.5 | C42—C43—H43 | 121.2 |
C26—C27—H27B | 109.5 | C44—C43—H43 | 121.2 |
H27A—C27—H27B | 109.5 | C45—C44—C43 | 121.3 (2) |
C26—C27—H27C | 109.5 | C45—C44—N42 | 119.4 (2) |
H27A—C27—H27C | 109.5 | C43—C44—N42 | 119.3 (2) |
H27B—C27—H27C | 109.5 | C44—C45—C46 | 120.2 (2) |
O32—N31—O33 | 123.4 (2) | C44—C45—H45 | 119.9 |
O32—N31—C32 | 119.1 (2) | C46—C45—H45 | 119.9 |
O33—N31—C32 | 117.5 (2) | C45—C46—C41 | 123.1 (2) |
O34—N32—O35 | 122.5 (2) | C45—C46—N43 | 116.4 (2) |
O34—N32—C34 | 118.3 (2) | C41—C46—N43 | 120.46 (19) |
O35—N32—C34 | 119.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O41 | 0.86 | 1.83 | 2.656 (3) | 160 |
N11—H11···O47 | 0.86 | 2.28 | 2.771 (5) | 117 |
N11—H11···O471 | 0.86 | 2.35 | 2.906 (11) | 123 |
N21—H21···O31 | 0.86 | 1.85 | 2.680 (3) | 160 |
N21—H21···O37 | 0.86 | 2.30 | 2.783 (3) | 116 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C5H10NO2+·C6H2N3O7− | C6H8N+·C6H2N3O7− |
Mr | 344.25 | 322.24 |
Crystal system, space group | MonoclinicP21 | TriclinicP1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.909 (4), 5.352 (3), 12.474 (5) | 8.211 (3), 11.806 (4), 14.388 (4) |
α, β, γ (°) | 90, 109.142 (5), 90 | 85.428 (5), 82.863 (5), 79.726 (4) |
V (Å3) | 688.0 (5) | 1359.4 (8) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.15 | 0.13 |
Crystal size (mm) | 0.3 × 0.2 × 0.12 | 0.25 × 0.2 × 0.15 |
Data collection | ||
Diffractometer | Nonius MACH3 sealed tube diffractometer | Nonius MACH3 sealed tube diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.967, 0.981 | 0.970, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3719, 2205, 1590 | 5848, 4762, 3255 |
Rint | 0.100 | 0.015 |
(sin θ/λ)max (Å−1) | 0.703 | 0.594 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.169, 1.07 | 0.042, 0.124, 1.04 |
No. of reflections | 2205 | 4762 |
No. of parameters | 226 | 426 |
No. of restraints | 10 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.27 | 0.32, −0.27 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SHELXTL/PC (Bruker, 2000), SHELXTL/PC, ORTEP 3 for Windows (Farrugia, 1997), PLATON (Spek, 2003) and Mercury (Version 1.4.1; Macrae et al., 2006).
O1A—C1 | 1.202 (4) | C5—N1 | 1.497 (5) |
O1B—C1 | 1.308 (4) | O11—C11 | 1.255 (4) |
C2—N1 | 1.493 (4) | ||
C2—N1—C5 | 107.1 (3) | ||
O1A—C1—C2—N1 | 19.1 (5) | O13—N11—C12—C13 | −42.6 (4) |
O1B—C1—C2—N1 | −163.0 (3) | O12—N11—C12—C11 | −41.3 (4) |
N1—C2—C3—C4 | 8.2 (6) | O15—N12—C14—C15 | 8.1 (5) |
C2—C3—C4—C5 | −27.1 (8) | O14—N12—C14—C13 | 11.5 (5) |
C3—C4—C5—N1 | 34.7 (9) | O16—N13—C16—C15 | −16.1 (4) |
C3—C2—N1—C5 | 11.8 (5) | O17—N13—C16—C11 | −16.6 (5) |
C4—C5—N1—C2 | −29.5 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1B—H1B···O11 | 0.82 | 1.71 | 2.515 (4) | 165.3 |
N1—H1C···O11i | 0.90 | 2.20 | 2.952 (4) | 140.9 |
N1—H1A···O17ii | 0.90 | 2.38 | 3.202 (5) | 152.8 |
N1—H1C···O17i | 0.90 | 2.37 | 3.106 (5) | 139.2 |
Symmetry codes: (i) −x+1, y−1/2, −z+2; (ii) −x+1, y−3/2, −z+2. |
N11—C12 | 1.324 (3) | O31—C31 | 1.252 (3) |
N11—C16 | 1.335 (3) | O41—C41 | 1.253 (3) |
C12—N11—C16 | 123.3 (2) | C22—N21—C26 | 123.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O41 | 0.86 | 1.83 | 2.656 (3) | 159.7 |
N11—H11···O47 | 0.86 | 2.28 | 2.771 (5) | 116.5 |
N11—H11···O471 | 0.86 | 2.35 | 2.906 (11) | 122.6 |
N21—H21···O31 | 0.86 | 1.85 | 2.680 (3) | 160.1 |
N21—H21···O37 | 0.86 | 2.30 | 2.783 (3) | 115.6 |
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Picric acid forms charge-transfer complexes with organic compounds. Crystalline picrates have commonly been used in the preparation of amine derivatives in qualitative organic chemistry (Shriner et al., 1980). The crystal structure elucidation of L-prolinium picrate, (I), and 2-methylpyridinium picrate, (II), was undertaken to study the nature of hydrogen bonding between the molecular ions, involving phenolate O atoms and the protonated N atoms, and the crystal packing in the different environments.
In the structure of (I), the asymmetric part of the unit cell contains a prolinium cation and a picrate anion (Fig. 1). An orthorhombic form of L-prolinium picrate has already been reported (Jin et al., 2003). The backbone conformation angles ψ1 (O1A—C1—C2—N1) and ψ2 (O1B—C1—C2—N1) are cis and trans, respectively. The side-chain conformation angles χ1 (N1—C2—C3—C4), χ2 (C2—C3—C4—C5), χ3 (C4—C5—N1—C2), χ4 (C3—C4—C5—N1) and θ (C4—C5—N1—C5) are 8.3, -27.2, -29.6, 34.7 and 13.2, respectively (Prasad & Vijayan, 1993) (Table 1). The Cγ atom (C4) of the pyrolidine ring has conformational disorder, as observed in bis(L-proline) hydrogen perchlorate (Pandiarajan et al., 2002). Atoms C4 and C41 deviate from the plane of which atoms?, whereas atoms N1, C2, C3 and C5 are nearly coplanar. Both major and minor conformers of the pyrrolidine ring adopt conformations intermediate between a half-chair and an envelope (Cremer & Pople, 1975; Nardelli, 1983). The angle between the rings of the anion and cation is 44.4 (2)°.
Both the cation and anion of (I) are packed through chelated three-centred N—H···O hydrogen bonds, as observed in other picrate complexes (Jin et al., 2003; Kai et al., 1994). The prolinium cation connects two different picrate anions, leading to an infinite chain running along the b axis (Fig. 2). Weak three-centred C—H···O hydrogen bonds also stabilize the structure. The prolinium cation forms an infinite chain along the b axis through a C—H···O hydrogen bond (Table 2). The anion and cation form a hydrogen-bonded network with a graph-set motif of R21(6) (Etter et al., 1990) (Fig. 2).
We now discuss the crystal structure of (II). The crystal structures of pyridine and pyridine trihydrate (Mootz & Wussow, 1981), pyridine picrate (Talukdar & Chaudhuri, 1976) and pyridinium picrate (Takayanagi et al., 1990) have already been reported. The asymmetric part of the unit cell of (II) contains two 2-methylpyridinium cations and two picrate anions (Fig. 4). The protonation of the N atom of the pyridine ring is confirmed from the values of the C—N bond distances, which agree well with those in pyridinum picrate (Table ? No values were flagged in the CIF for inclusion in a bond table - do you wish to add them?). The angles between the rings of both anions and those of the cations are 74.4 (1) and 79.4 (1)°, and 76.5 (1) and 80.7 (1)° [It is not clear which pairs of rings these are angles between - please clarify]. The pyridine ring is almost normal to the phenyl ring. This fact supports the absence of π bonding in this complex, as observed in p-phenylenediamine picrate and o-phenylenediamine picrate (Takayanagi et al., 1996). Both cations form bifurcated N—H···O hydrogen bonds with inversely related anions, thus forming a graph-set motif of R21(6) (Etter et al., 1990) (Fig. 5). This type of bifurcated hydrogen bonding (Table 3) is also observed in the crystal structure of (I).
In the picrate anions of (I) and (II), the bond distances and angles show the deprotonation of the phenolic group, and the geometry is similar to that in other picrate complexes (Takayanagi et al., 1996). The picrate anions are sandwiched between layers of prolinium cations along the c axis in (I) (Fig. 3), whereas in (II), the picrate anions are packed between layers of pyridinium cations (Fig. 5). In the structure of (II), both the anions are arranged nearly parallel to each other, making angles of 9.02 (1) and 11.4 (1)° with the [001] plane. Intramolecular contacts between the phenolate O atoms and adjacent nitro groups are observed in both structures. In compounds (I) and (II), one of the ortho-nitro groups is twisted more from the plane of the ring, while the para-nitro group is nearly planar. In the structure of (II), the angle between the rings of the picrate anions is 20.6 (1)°, and the angle between the rings of the pyridinium cations is 25.1 (1)°.