At one extreme of the proton-transfer spectrum in cocrystals, proton transfer is absent, whilst at the opposite extreme, in salts, the proton-transfer process is complete. However, for acid–base pairs with a small ΔpKa (pKa of base − pKa of acid), prediction of the extent of proton transfer is not possible as there is a continuum between the salt and cocrystal ends. In this context, we attempt to illustrate that in these systems, in addition to ΔpKa, the crystalline environment could change the extent of proton transfer. To this end, two compounds of salicylic acid (SaH) and adenine (Ad) have been prepared. Despite the same small ΔpKa value (≈1.2), different ionization states are found. Both crystals, namely adeninium salicylate monohydrate, C5H6N5+·C7H5O3−·H2O, I, and adeninium salicylate–adenine–salicylic acid–water (1/2/1/2), C5H6N5+·C7H5O3−·2C5H5N5·C7H6O3·2H2O, II, have been characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis (C, H and N) techniques. In addition, the intermolecular hydrogen-bonding interactions of compounds I and II have been investigated and quantified in detail on the basis of Hirshfeld surface analysis and fingerprint plots. Throughout the study, we use crystal engineering, which is based on modifications of the intermolecular interactions, thus offering a more comprehensive screening of the salt–cocrystal continuum in comparison with pure pKa analysis.
Supporting information
CCDC references: 1873134; 1873133
Data collection: CrysAlis CCD (Rigaku OD, 2015 for COMP_I; CrysAlis CCD (Rigaku OD, 2015) for COMP_II. For both structures, cell refinement: CrysAlis RED (Rigaku OD, 2015); data reduction: CrysAlis RED (Rigaku OD, 2015). Program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a) for COMP_I; SHELXT (Sheldrick, 2015a) for COMP_II. For both structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).
Adeninium salicylate monohydrate (COMP_I)
top
Crystal data top
C5H6N5+·C7H5O3−·H2O | Z = 4 |
Mr = 291.27 | F(000) = 608 |
Triclinic, P1 | Dx = 1.497 Mg m−3 |
a = 7.2329 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.4405 (7) Å | Cell parameters from 2470 reflections |
c = 14.7468 (8) Å | θ = 3.3–26.1° |
α = 82.507 (4)° | µ = 0.12 mm−1 |
β = 79.385 (6)° | T = 100 K |
γ = 86.828 (5)° | Needle, colourless |
V = 1292.42 (14) Å3 | 0.23 × 0.11 × 0.08 mm |
Data collection top
Kuma KM-4 with CCD detector diffractometer | 5357 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2777 reflections with I > 2σ(I) |
Detector resolution: 10.6249 pixels mm-1 | Rint = 0.091 |
ω–scan | θmax = 26.5°, θmin = 2.8° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | h = −9→9 |
Tmin = 0.982, Tmax = 1.000 | k = −15→15 |
27185 measured reflections | l = −18→18 |
Refinement top
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)] = 0.066 | Hydrogen site location: mixed |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3 |
5357 reflections | (Δ/σ)max = 0.001 |
415 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0998 (4) | 0.7395 (2) | −0.07331 (19) | 0.0179 (7) | |
C2 | 0.0963 (4) | 0.8214 (2) | −0.1473 (2) | 0.0237 (7) | |
C3 | 0.0646 (4) | 0.7957 (2) | −0.2338 (2) | 0.0278 (8) | |
H3 | 0.060306 | 0.851171 | −0.284200 | 0.033* | |
C4 | 0.0399 (4) | 0.6889 (2) | −0.2441 (2) | 0.0268 (8) | |
H4 | 0.020921 | 0.671305 | −0.302370 | 0.032* | |
C5 | 0.0423 (4) | 0.6063 (2) | −0.1702 (2) | 0.0266 (8) | |
H5 | 0.023052 | 0.533454 | −0.178096 | 0.032* | |
C6 | 0.0731 (4) | 0.6315 (2) | −0.0857 (2) | 0.0246 (7) | |
H6 | 0.076148 | 0.575483 | −0.035565 | 0.030* | |
C7 | 0.1389 (4) | 0.7641 (2) | 0.0173 (2) | 0.0219 (7) | |
O1 | 0.1677 (3) | 0.86069 (15) | 0.02821 (14) | 0.0286 (5) | |
O2 | 0.1440 (3) | 0.68351 (15) | 0.08059 (14) | 0.0263 (5) | |
O3 | 0.1224 (3) | 0.92645 (16) | −0.13982 (16) | 0.0401 (6) | |
H3O | 0.159 (4) | 0.924 (3) | −0.073 (2) | 0.060* | |
C11 | 0.1972 (4) | 0.2541 (2) | 0.6302 (2) | 0.0200 (7) | |
C12 | 0.1721 (4) | 0.1472 (2) | 0.6135 (2) | 0.0193 (7) | |
C13 | 0.1539 (4) | 0.1258 (2) | 0.5259 (2) | 0.0222 (7) | |
H13 | 0.140833 | 0.053246 | 0.514886 | 0.027* | |
C14 | 0.1546 (4) | 0.2088 (2) | 0.4549 (2) | 0.0248 (7) | |
H14 | 0.143371 | 0.193229 | 0.394790 | 0.030* | |
C15 | 0.1717 (4) | 0.3161 (2) | 0.4700 (2) | 0.0256 (7) | |
H15 | 0.169445 | 0.373706 | 0.421071 | 0.031* | |
C16 | 0.1918 (4) | 0.3369 (2) | 0.5567 (2) | 0.0238 (7) | |
H16 | 0.202458 | 0.409836 | 0.567112 | 0.029* | |
C17 | 0.2299 (4) | 0.2771 (2) | 0.7231 (2) | 0.0208 (7) | |
O11 | 0.2580 (3) | 0.37330 (15) | 0.73554 (13) | 0.0263 (5) | |
O12 | 0.2266 (3) | 0.19721 (15) | 0.78684 (13) | 0.0247 (5) | |
O13 | 0.1652 (3) | 0.06232 (16) | 0.68184 (15) | 0.0276 (5) | |
H13O | 0.185 (4) | 0.090 (2) | 0.736 (2) | 0.041* | |
C21 | 0.2635 (4) | 0.8034 (2) | 0.2634 (2) | 0.0199 (7) | |
N22 | 0.2284 (3) | 0.70744 (19) | 0.23615 (17) | 0.0226 (6) | |
H22 | 0.209 (4) | 0.706 (2) | 0.170 (2) | 0.027* | |
C23 | 0.2343 (4) | 0.6131 (2) | 0.2921 (2) | 0.0228 (7) | |
H23 | 0.211383 | 0.549597 | 0.267038 | 0.027* | |
N24 | 0.2683 (3) | 0.59907 (18) | 0.37781 (17) | 0.0213 (6) | |
C25 | 0.2988 (4) | 0.6959 (2) | 0.4056 (2) | 0.0201 (7) | |
N26 | 0.3370 (3) | 0.71268 (19) | 0.48976 (17) | 0.0209 (6) | |
H26 | 0.352 (4) | 0.667 (2) | 0.5398 (19) | 0.025* | |
C27 | 0.3585 (4) | 0.8212 (2) | 0.4849 (2) | 0.0221 (7) | |
H27 | 0.386767 | 0.854246 | 0.535114 | 0.027* | |
N28 | 0.3370 (3) | 0.87668 (18) | 0.40549 (17) | 0.0233 (6) | |
C29 | 0.2992 (4) | 0.7970 (2) | 0.3537 (2) | 0.0199 (7) | |
N30 | 0.2614 (4) | 0.8925 (2) | 0.20328 (19) | 0.0273 (7) | |
H30A | 0.230 (4) | 0.886 (2) | 0.151 (2) | 0.033* | |
H30B | 0.286 (4) | 0.955 (2) | 0.218 (2) | 0.033* | |
C31 | 0.3747 (4) | 0.3116 (2) | 0.9692 (2) | 0.0197 (7) | |
N32 | 0.3301 (3) | 0.21236 (18) | 0.94933 (17) | 0.0196 (6) | |
H32 | 0.300 (3) | 0.211 (2) | 0.8875 (19) | 0.023* | |
C33 | 0.3297 (4) | 0.1199 (2) | 1.0092 (2) | 0.0234 (7) | |
H33 | 0.299093 | 0.055115 | 0.988259 | 0.028* | |
N34 | 0.3673 (3) | 0.11196 (17) | 1.09251 (17) | 0.0225 (6) | |
C35 | 0.4076 (4) | 0.2091 (2) | 1.11553 (19) | 0.0167 (7) | |
N36 | 0.4489 (3) | 0.22995 (19) | 1.19730 (18) | 0.0228 (6) | |
H36 | 0.465 (4) | 0.181 (2) | 1.242 (2) | 0.027* | |
C37 | 0.4802 (4) | 0.3380 (2) | 1.1888 (2) | 0.0215 (7) | |
H37 | 0.512706 | 0.372796 | 1.237099 | 0.026* | |
N38 | 0.4607 (3) | 0.38987 (17) | 1.10652 (16) | 0.0203 (6) | |
C39 | 0.4148 (4) | 0.3085 (2) | 1.0592 (2) | 0.0195 (7) | |
N40 | 0.3718 (3) | 0.39732 (19) | 0.90723 (18) | 0.0211 (6) | |
H40A | 0.339 (4) | 0.393 (2) | 0.848 (2) | 0.025* | |
H40B | 0.419 (4) | 0.458 (2) | 0.9200 (18) | 0.025* | |
O1W | 0.4158 (3) | 0.55525 (14) | 0.62864 (15) | 0.0272 (5) | |
H1W1 | 0.521711 | 0.525156 | 0.616369 | 0.041* | |
H2W1 | 0.345274 | 0.503857 | 0.654402 | 0.041* | |
O2W | 0.5113 (3) | 0.07390 (14) | 1.33830 (16) | 0.0282 (5) | |
H1W2 | 0.609376 | 0.041407 | 1.315705 | 0.042* | |
H2W2 | 0.435551 | 0.023731 | 1.359483 | 0.042* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0194 (17) | 0.0189 (16) | 0.0149 (16) | −0.0014 (12) | −0.0001 (13) | −0.0043 (13) |
C2 | 0.0232 (18) | 0.0180 (17) | 0.032 (2) | −0.0054 (13) | −0.0042 (15) | −0.0082 (14) |
C3 | 0.0270 (19) | 0.0321 (19) | 0.0258 (19) | −0.0041 (14) | −0.0097 (15) | −0.0010 (15) |
C4 | 0.0263 (19) | 0.0315 (19) | 0.0279 (19) | 0.0001 (14) | −0.0113 (15) | −0.0140 (16) |
C5 | 0.0224 (18) | 0.0249 (18) | 0.036 (2) | 0.0008 (13) | −0.0096 (15) | −0.0094 (15) |
C6 | 0.0226 (18) | 0.0248 (18) | 0.0279 (19) | −0.0032 (13) | −0.0023 (15) | −0.0105 (14) |
C7 | 0.0193 (17) | 0.0224 (18) | 0.0234 (18) | −0.0054 (13) | −0.0004 (14) | −0.0037 (15) |
O1 | 0.0398 (14) | 0.0199 (12) | 0.0281 (13) | −0.0050 (10) | −0.0100 (11) | −0.0033 (10) |
O2 | 0.0359 (13) | 0.0221 (12) | 0.0220 (12) | −0.0036 (9) | −0.0075 (10) | −0.0023 (10) |
O3 | 0.0602 (17) | 0.0259 (13) | 0.0387 (15) | −0.0135 (11) | −0.0209 (13) | 0.0013 (11) |
C11 | 0.0174 (17) | 0.0198 (17) | 0.0236 (18) | −0.0023 (13) | −0.0028 (14) | −0.0065 (14) |
C12 | 0.0195 (17) | 0.0156 (16) | 0.0229 (17) | 0.0025 (12) | −0.0069 (14) | 0.0009 (14) |
C13 | 0.0189 (17) | 0.0230 (17) | 0.0270 (19) | −0.0008 (13) | −0.0047 (14) | −0.0106 (14) |
C14 | 0.0234 (18) | 0.0302 (19) | 0.0230 (18) | −0.0027 (14) | −0.0077 (14) | −0.0056 (15) |
C15 | 0.0247 (18) | 0.0291 (18) | 0.0248 (18) | −0.0063 (14) | −0.0102 (15) | 0.0007 (14) |
C16 | 0.0195 (17) | 0.0219 (17) | 0.0307 (19) | −0.0023 (13) | −0.0054 (15) | −0.0037 (15) |
C17 | 0.0151 (16) | 0.0258 (18) | 0.0216 (18) | −0.0032 (13) | −0.0011 (13) | −0.0061 (15) |
O11 | 0.0358 (13) | 0.0192 (12) | 0.0253 (13) | −0.0073 (9) | −0.0052 (10) | −0.0052 (9) |
O12 | 0.0324 (13) | 0.0224 (12) | 0.0212 (12) | −0.0043 (9) | −0.0079 (10) | −0.0037 (10) |
O13 | 0.0387 (13) | 0.0215 (12) | 0.0239 (13) | −0.0031 (9) | −0.0052 (11) | −0.0071 (10) |
C21 | 0.0177 (17) | 0.0167 (17) | 0.0233 (18) | −0.0006 (12) | −0.0003 (14) | 0.0004 (14) |
N22 | 0.0307 (16) | 0.0182 (14) | 0.0206 (15) | −0.0008 (11) | −0.0060 (12) | −0.0062 (12) |
C23 | 0.0247 (18) | 0.0183 (17) | 0.0270 (19) | 0.0007 (13) | −0.0030 (15) | −0.0113 (14) |
N24 | 0.0234 (15) | 0.0195 (14) | 0.0228 (15) | −0.0003 (11) | −0.0066 (12) | −0.0057 (11) |
C25 | 0.0145 (16) | 0.0225 (17) | 0.0236 (18) | −0.0007 (12) | −0.0045 (14) | −0.0025 (14) |
N26 | 0.0246 (15) | 0.0185 (14) | 0.0207 (15) | 0.0003 (11) | −0.0101 (12) | 0.0018 (11) |
C27 | 0.0184 (17) | 0.0219 (18) | 0.0289 (19) | −0.0003 (13) | −0.0048 (14) | −0.0134 (15) |
N28 | 0.0263 (15) | 0.0211 (14) | 0.0241 (15) | −0.0050 (11) | −0.0059 (12) | −0.0051 (12) |
C29 | 0.0146 (16) | 0.0188 (17) | 0.0254 (18) | −0.0011 (12) | −0.0013 (14) | −0.0031 (14) |
N30 | 0.0403 (18) | 0.0198 (15) | 0.0236 (16) | −0.0036 (12) | −0.0096 (14) | −0.0026 (13) |
C31 | 0.0149 (16) | 0.0210 (17) | 0.0243 (18) | −0.0009 (12) | −0.0022 (14) | −0.0081 (14) |
N32 | 0.0243 (15) | 0.0170 (14) | 0.0205 (15) | −0.0032 (10) | −0.0095 (12) | −0.0049 (12) |
C33 | 0.0286 (19) | 0.0138 (16) | 0.0299 (19) | −0.0060 (13) | −0.0066 (15) | −0.0056 (14) |
N34 | 0.0263 (15) | 0.0155 (14) | 0.0266 (16) | −0.0039 (11) | −0.0065 (12) | −0.0022 (12) |
C35 | 0.0178 (16) | 0.0175 (16) | 0.0144 (16) | −0.0032 (12) | −0.0005 (13) | −0.0034 (13) |
N36 | 0.0249 (15) | 0.0205 (15) | 0.0230 (16) | −0.0036 (11) | −0.0061 (12) | 0.0013 (11) |
C37 | 0.0228 (18) | 0.0197 (17) | 0.0238 (18) | −0.0004 (13) | −0.0052 (14) | −0.0083 (14) |
N38 | 0.0263 (15) | 0.0181 (14) | 0.0187 (14) | −0.0017 (11) | −0.0077 (12) | −0.0045 (11) |
C39 | 0.0171 (16) | 0.0153 (16) | 0.0272 (18) | −0.0036 (12) | −0.0025 (14) | −0.0077 (13) |
N40 | 0.0333 (16) | 0.0126 (14) | 0.0194 (15) | −0.0075 (11) | −0.0085 (12) | −0.0011 (12) |
O1W | 0.0314 (13) | 0.0194 (12) | 0.0314 (14) | −0.0025 (9) | −0.0076 (11) | −0.0011 (10) |
O2W | 0.0317 (13) | 0.0179 (12) | 0.0325 (14) | −0.0006 (9) | −0.0015 (11) | 0.0000 (10) |
Geometric parameters (Å, º) top
C1—C2 | 1.396 (4) | N22—H22 | 1.02 (3) |
C1—C6 | 1.407 (4) | C23—N24 | 1.319 (3) |
C1—C7 | 1.488 (4) | C23—H23 | 0.9500 |
C2—O3 | 1.352 (3) | N24—C25 | 1.363 (3) |
C2—C3 | 1.416 (4) | C25—N26 | 1.364 (3) |
C3—C4 | 1.380 (4) | C25—C29 | 1.384 (4) |
C3—H3 | 0.9500 | N26—C27 | 1.359 (3) |
C4—C5 | 1.398 (4) | N26—H26 | 0.89 (3) |
C4—H4 | 0.9500 | C27—N28 | 1.310 (3) |
C5—C6 | 1.384 (4) | C27—H27 | 0.9500 |
C5—H5 | 0.9500 | N28—C29 | 1.395 (3) |
C6—H6 | 0.9500 | N30—H30A | 0.85 (3) |
C7—O1 | 1.266 (3) | N30—H30B | 0.87 (3) |
C7—O2 | 1.282 (3) | C31—N40 | 1.313 (3) |
O3—H3O | 1.06 (3) | C31—N32 | 1.373 (3) |
C11—C16 | 1.399 (4) | C31—C39 | 1.405 (4) |
C11—C12 | 1.411 (4) | N32—C33 | 1.356 (3) |
C11—C17 | 1.498 (4) | N32—H32 | 0.98 (3) |
C12—O13 | 1.357 (3) | C33—N34 | 1.297 (3) |
C12—C13 | 1.384 (4) | C33—H33 | 0.9500 |
C13—C14 | 1.371 (4) | N34—C35 | 1.358 (3) |
C13—H13 | 0.9500 | C35—N36 | 1.354 (3) |
C14—C15 | 1.398 (4) | C35—C39 | 1.395 (4) |
C14—H14 | 0.9500 | N36—C37 | 1.361 (3) |
C15—C16 | 1.371 (4) | N36—H36 | 0.86 (3) |
C15—H15 | 0.9500 | C37—N38 | 1.326 (3) |
C16—H16 | 0.9500 | C37—H37 | 0.9500 |
C17—O11 | 1.267 (3) | N38—C39 | 1.388 (3) |
C17—O12 | 1.274 (3) | N40—H40A | 0.96 (3) |
O13—H13O | 0.94 (3) | N40—H40B | 0.90 (3) |
C21—N30 | 1.327 (4) | O1W—H1W1 | 0.8334 |
C21—N22 | 1.360 (3) | O1W—H2W1 | 0.8455 |
C21—C29 | 1.394 (4) | O2W—H1W2 | 0.8333 |
N22—C23 | 1.347 (3) | O2W—H2W2 | 0.8432 |
| | | |
C2—C1—C6 | 119.5 (3) | C21—N22—H22 | 119.3 (15) |
C2—C1—C7 | 120.9 (2) | N24—C23—N22 | 127.3 (3) |
C6—C1—C7 | 119.5 (3) | N24—C23—H23 | 116.3 |
O3—C2—C1 | 122.2 (3) | N22—C23—H23 | 116.3 |
O3—C2—C3 | 117.8 (3) | C23—N24—C25 | 110.7 (2) |
C1—C2—C3 | 120.0 (3) | N24—C25—N26 | 127.0 (3) |
C4—C3—C2 | 119.2 (3) | N24—C25—C29 | 126.9 (3) |
C4—C3—H3 | 120.4 | N26—C25—C29 | 106.1 (2) |
C2—C3—H3 | 120.4 | C27—N26—C25 | 105.9 (2) |
C3—C4—C5 | 121.2 (3) | C27—N26—H26 | 121.9 (17) |
C3—C4—H4 | 119.4 | C25—N26—H26 | 132.2 (17) |
C5—C4—H4 | 119.4 | N28—C27—N26 | 114.6 (3) |
C6—C5—C4 | 119.5 (3) | N28—C27—H27 | 122.7 |
C6—C5—H5 | 120.2 | N26—C27—H27 | 122.7 |
C4—C5—H5 | 120.2 | C27—N28—C29 | 103.1 (2) |
C5—C6—C1 | 120.5 (3) | C25—C29—N28 | 110.3 (2) |
C5—C6—H6 | 119.7 | C25—C29—C21 | 118.1 (3) |
C1—C6—H6 | 119.7 | N28—C29—C21 | 131.5 (3) |
O1—C7—O2 | 123.4 (3) | C21—N30—H30A | 117 (2) |
O1—C7—C1 | 119.9 (3) | C21—N30—H30B | 120.6 (19) |
O2—C7—C1 | 116.7 (2) | H30A—N30—H30B | 122 (3) |
C2—O3—H3O | 103.8 (17) | N40—C31—N32 | 119.8 (3) |
C16—C11—C12 | 117.4 (3) | N40—C31—C39 | 126.9 (3) |
C16—C11—C17 | 121.7 (3) | N32—C31—C39 | 113.3 (3) |
C12—C11—C17 | 120.9 (3) | C33—N32—C31 | 123.7 (3) |
O13—C12—C13 | 117.8 (2) | C33—N32—H32 | 120.4 (15) |
O13—C12—C11 | 121.7 (3) | C31—N32—H32 | 115.9 (15) |
C13—C12—C11 | 120.5 (3) | N34—C33—N32 | 125.7 (3) |
C14—C13—C12 | 120.3 (3) | N34—C33—H33 | 117.1 |
C14—C13—H13 | 119.9 | N32—C33—H33 | 117.1 |
C12—C13—H13 | 119.9 | C33—N34—C35 | 112.2 (2) |
C13—C14—C15 | 120.7 (3) | N36—C35—N34 | 127.5 (3) |
C13—C14—H14 | 119.7 | N36—C35—C39 | 105.7 (2) |
C15—C14—H14 | 119.7 | N34—C35—C39 | 126.8 (3) |
C16—C15—C14 | 118.9 (3) | C35—N36—C37 | 107.1 (2) |
C16—C15—H15 | 120.6 | C35—N36—H36 | 124.4 (19) |
C14—C15—H15 | 120.6 | C37—N36—H36 | 128.1 (19) |
C15—C16—C11 | 122.2 (3) | N38—C37—N36 | 113.3 (2) |
C15—C16—H16 | 118.9 | N38—C37—H37 | 123.4 |
C11—C16—H16 | 118.9 | N36—C37—H37 | 123.4 |
O11—C17—O12 | 123.0 (3) | C37—N38—C39 | 103.5 (2) |
O11—C17—C11 | 119.7 (3) | N38—C39—C35 | 110.4 (2) |
O12—C17—C11 | 117.3 (3) | N38—C39—C31 | 131.4 (3) |
C12—O13—H13O | 107.3 (18) | C35—C39—C31 | 118.2 (2) |
N30—C21—N22 | 118.3 (3) | C31—N40—H40A | 121.5 (15) |
N30—C21—C29 | 126.5 (3) | C31—N40—H40B | 116.4 (17) |
N22—C21—C29 | 115.2 (3) | H40A—N40—H40B | 121 (2) |
C23—N22—C21 | 121.7 (3) | H1W1—O1W—H2W1 | 103.9 |
C23—N22—H22 | 118.8 (15) | H1W2—O2W—H2W2 | 103.8 |
| | | |
C6—C1—C2—O3 | −179.5 (3) | C23—N24—C25—C29 | −1.1 (4) |
C7—C1—C2—O3 | −2.0 (4) | N24—C25—N26—C27 | 179.3 (3) |
C6—C1—C2—C3 | 0.5 (4) | C29—C25—N26—C27 | −0.1 (3) |
C7—C1—C2—C3 | 178.0 (3) | C25—N26—C27—N28 | 0.3 (3) |
O3—C2—C3—C4 | 179.1 (3) | N26—C27—N28—C29 | −0.4 (3) |
C1—C2—C3—C4 | −0.9 (4) | N24—C25—C29—N28 | −179.6 (3) |
C2—C3—C4—C5 | 1.2 (4) | N26—C25—C29—N28 | −0.1 (3) |
C3—C4—C5—C6 | −1.1 (4) | N24—C25—C29—C21 | 0.6 (4) |
C4—C5—C6—C1 | 0.7 (4) | N26—C25—C29—C21 | 180.0 (3) |
C2—C1—C6—C5 | −0.4 (4) | C27—N28—C29—C25 | 0.3 (3) |
C7—C1—C6—C5 | −178.0 (3) | C27—N28—C29—C21 | −179.9 (3) |
C2—C1—C7—O1 | 0.8 (4) | N30—C21—C29—C25 | −178.7 (3) |
C6—C1—C7—O1 | 178.3 (3) | N22—C21—C29—C25 | 1.1 (4) |
C2—C1—C7—O2 | −178.3 (3) | N30—C21—C29—N28 | 1.4 (5) |
C6—C1—C7—O2 | −0.8 (4) | N22—C21—C29—N28 | −178.8 (3) |
C16—C11—C12—O13 | −176.5 (3) | N40—C31—N32—C33 | 179.9 (3) |
C17—C11—C12—O13 | 4.1 (4) | C39—C31—N32—C33 | −1.7 (4) |
C16—C11—C12—C13 | 3.6 (4) | C31—N32—C33—N34 | 1.2 (5) |
C17—C11—C12—C13 | −175.9 (3) | N32—C33—N34—C35 | 0.5 (4) |
O13—C12—C13—C14 | 178.2 (2) | C33—N34—C35—N36 | 178.5 (3) |
C11—C12—C13—C14 | −1.9 (4) | C33—N34—C35—C39 | −1.5 (4) |
C12—C13—C14—C15 | −0.7 (4) | N34—C35—N36—C37 | 179.7 (3) |
C13—C14—C15—C16 | 1.4 (4) | C39—C35—N36—C37 | −0.3 (3) |
C14—C15—C16—C11 | 0.5 (4) | C35—N36—C37—N38 | 0.4 (3) |
C12—C11—C16—C15 | −2.9 (4) | N36—C37—N38—C39 | −0.4 (3) |
C17—C11—C16—C15 | 176.6 (3) | C37—N38—C39—C35 | 0.2 (3) |
C16—C11—C17—O11 | −1.7 (4) | C37—N38—C39—C31 | 179.2 (3) |
C12—C11—C17—O11 | 177.7 (2) | N36—C35—C39—N38 | 0.1 (3) |
C16—C11—C17—O12 | 177.9 (3) | N34—C35—C39—N38 | −179.9 (3) |
C12—C11—C17—O12 | −2.7 (4) | N36—C35—C39—C31 | −179.1 (3) |
N30—C21—N22—C23 | 177.7 (3) | N34—C35—C39—C31 | 0.9 (4) |
C29—C21—N22—C23 | −2.1 (4) | N40—C31—C39—N38 | −0.1 (5) |
C21—N22—C23—N24 | 1.7 (5) | N32—C31—C39—N38 | −178.3 (3) |
N22—C23—N24—C25 | 0.0 (4) | N40—C31—C39—C35 | 179.0 (3) |
C23—N24—C25—N26 | 179.6 (3) | N32—C31—C39—C35 | 0.8 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O1 | 1.06 (3) | 1.61 (3) | 2.580 (3) | 150 (3) |
O13—H13O···O12 | 0.94 (3) | 1.68 (3) | 2.535 (3) | 148 (3) |
N22—H22···O2 | 1.02 (3) | 1.53 (3) | 2.537 (3) | 166 (2) |
N26—H26···O1W | 0.89 (3) | 1.88 (3) | 2.760 (3) | 169 (3) |
C27—H27···O2Wi | 0.95 | 2.42 | 3.363 (4) | 174 |
N30—H30A···O1 | 0.85 (3) | 2.02 (3) | 2.867 (3) | 176 (3) |
N30—H30B···N34ii | 0.87 (3) | 2.52 (3) | 3.052 (3) | 120 (2) |
N32—H32···O12 | 0.98 (3) | 1.70 (3) | 2.670 (3) | 173 (2) |
C33—H33···O1iii | 0.95 | 2.60 | 3.451 (3) | 149 |
N36—H36···O2W | 0.86 (3) | 1.88 (3) | 2.737 (3) | 178 (3) |
C37—H37···O1Wi | 0.95 | 2.42 | 3.371 (4) | 174 |
N40—H40A···O11 | 0.96 (3) | 1.90 (3) | 2.858 (3) | 175 (2) |
N40—H40B···N38i | 0.90 (3) | 2.09 (3) | 2.940 (3) | 158 (2) |
O1W—H1W1···N24iv | 0.83 | 2.11 | 2.898 (3) | 157 |
O1W—H2W1···O11 | 0.85 | 1.95 | 2.758 (3) | 160 |
O2W—H1W2···O13v | 0.83 | 2.03 | 2.806 (3) | 156 |
O2W—H2W2···N28iii | 0.84 | 1.99 | 2.800 (3) | 161 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y+1, z−1; (iii) x, y−1, z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+2. |
Adeninium salicylate–adenine–salicylic acid–water (1/2/1/2) (COMP_II)
top
Crystal data top
C5H6N5+·C7H5O3−·2C5H5N5·C7H6O3·2H2O | F(000) = 1496 |
Mr = 717.69 | Dx = 1.483 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 22.335 (2) Å | Cell parameters from 1871 reflections |
b = 4.8497 (4) Å | θ = 2.8–26.2° |
c = 31.567 (3) Å | µ = 0.11 mm−1 |
β = 109.936 (9)° | T = 100 K |
V = 3214.4 (6) Å3 | Needle, colourless |
Z = 4 | 0.26 × 0.18 × 0.12 mm |
Data collection top
Kuma KM-4 with CCD detector diffractometer | 6457 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 3318 reflections with I > 2σ(I) |
Detector resolution: 10.6249 pixels mm-1 | Rint = 0.063 |
ω–scan | θmax = 26.5°, θmin = 2.6° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | h = −27→28 |
Tmin = 0.981, Tmax = 1.000 | k = −6→6 |
31280 measured reflections | l = −39→39 |
Refinement top
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)] = 0.075 | Hydrogen site location: mixed |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0152P)2] where P = (Fo2 + 2Fc2)/3 |
6457 reflections | (Δ/σ)max = 0.001 |
514 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.20080 (16) | −1.2519 (6) | 0.43125 (11) | 0.0193 (8) | |
C2 | 0.14835 (17) | −1.2842 (6) | 0.39250 (12) | 0.0217 (8) | |
C3 | 0.10092 (17) | −1.4761 (7) | 0.39024 (13) | 0.0286 (9) | |
H3 | 0.064878 | −1.494351 | 0.363562 | 0.034* | |
C4 | 0.10701 (18) | −1.6385 (7) | 0.42711 (14) | 0.0316 (10) | |
H4 | 0.074409 | −1.767432 | 0.425820 | 0.038* | |
C5 | 0.15971 (18) | −1.6188 (7) | 0.46626 (13) | 0.0288 (10) | |
H5 | 0.163698 | −1.734683 | 0.491337 | 0.035* | |
C6 | 0.20647 (17) | −1.4257 (6) | 0.46796 (12) | 0.0251 (9) | |
H6 | 0.242920 | −1.411211 | 0.494437 | 0.030* | |
C7 | 0.25128 (17) | −1.0450 (7) | 0.43405 (13) | 0.0206 (8) | |
O1 | 0.24216 (10) | −0.8907 (4) | 0.39927 (8) | 0.0216 (6) | |
O2 | 0.29970 (11) | −1.0290 (4) | 0.46885 (8) | 0.0247 (6) | |
O3 | 0.13995 (11) | −1.1335 (5) | 0.35403 (9) | 0.0292 (7) | |
H3A | 0.1693 (17) | −1.002 (7) | 0.3613 (12) | 0.044* | |
C11 | 0.61234 (16) | 2.3071 (6) | 0.11017 (11) | 0.0192 (8) | |
C12 | 0.66820 (17) | 2.3781 (7) | 0.10148 (12) | 0.0238 (9) | |
C13 | 0.66538 (18) | 2.5738 (7) | 0.06838 (12) | 0.0286 (9) | |
H13 | 0.703026 | 2.621978 | 0.062488 | 0.034* | |
C14 | 0.60919 (19) | 2.6959 (7) | 0.04453 (12) | 0.0331 (10) | |
H14 | 0.607975 | 2.829965 | 0.022308 | 0.040* | |
C15 | 0.55309 (18) | 2.6259 (7) | 0.05242 (12) | 0.0329 (10) | |
H15 | 0.513941 | 2.711435 | 0.035555 | 0.039* | |
C16 | 0.55503 (17) | 2.4326 (7) | 0.08474 (12) | 0.0273 (9) | |
H16 | 0.516866 | 2.383680 | 0.089853 | 0.033* | |
C17 | 0.61545 (18) | 2.1071 (7) | 0.14615 (12) | 0.0231 (9) | |
O11 | 0.56015 (11) | 2.0284 (4) | 0.14773 (8) | 0.0238 (6) | |
H11 | 0.5657 (16) | 1.892 (6) | 0.1676 (11) | 0.036* | |
O12 | 0.66655 (12) | 2.0247 (5) | 0.17261 (8) | 0.0311 (7) | |
O13 | 0.72574 (12) | 2.2583 (5) | 0.12319 (8) | 0.0304 (7) | |
H13A | 0.7288 (17) | 2.138 (7) | 0.1460 (12) | 0.046* | |
C21 | 0.42850 (16) | −0.3061 (6) | 0.42841 (11) | 0.0192 (8) | |
N22 | 0.49074 (14) | −0.2542 (5) | 0.45400 (9) | 0.0254 (7) | |
C23 | 0.50670 (18) | −0.0528 (7) | 0.43125 (12) | 0.0264 (9) | |
H23 | 0.547708 | 0.029942 | 0.440625 | 0.032* | |
N24 | 0.45854 (14) | 0.0229 (6) | 0.39325 (10) | 0.0217 (7) | |
H24 | 0.4598 (14) | 0.164 (6) | 0.3722 (10) | 0.026* | |
C25 | 0.40816 (17) | −0.1383 (6) | 0.39060 (11) | 0.0182 (8) | |
N26 | 0.35023 (14) | −0.1313 (5) | 0.35784 (9) | 0.0218 (7) | |
C27 | 0.31162 (17) | −0.3180 (7) | 0.36474 (12) | 0.0228 (9) | |
H27 | 0.269782 | −0.328545 | 0.343305 | 0.027* | |
N28 | 0.32678 (14) | −0.4964 (6) | 0.39999 (10) | 0.0190 (7) | |
H28 | 0.2980 (14) | −0.629 (6) | 0.3996 (10) | 0.023* | |
C29 | 0.38464 (17) | −0.4969 (7) | 0.43391 (12) | 0.0211 (8) | |
N30 | 0.39555 (14) | −0.6706 (6) | 0.46788 (10) | 0.0225 (8) | |
H30A | 0.3643 (15) | −0.787 (6) | 0.4680 (10) | 0.027* | |
H30B | 0.4324 (15) | −0.663 (6) | 0.4901 (11) | 0.027* | |
C31 | 0.60073 (17) | 1.4984 (7) | 0.24087 (12) | 0.0226 (9) | |
N32 | 0.55973 (13) | 1.6262 (5) | 0.20248 (9) | 0.0205 (7) | |
C33 | 0.50459 (17) | 1.4972 (6) | 0.19494 (12) | 0.0224 (9) | |
H33 | 0.466820 | 1.540998 | 0.170690 | 0.027* | |
N34 | 0.50796 (14) | 1.2965 (5) | 0.22553 (10) | 0.0200 (7) | |
H34 | 0.4705 (14) | 1.193 (6) | 0.2230 (10) | 0.024* | |
C35 | 0.56832 (17) | 1.2942 (6) | 0.25515 (12) | 0.0191 (8) | |
N36 | 0.59293 (13) | 1.1347 (5) | 0.29232 (10) | 0.0217 (7) | |
C37 | 0.65379 (17) | 1.1989 (7) | 0.31469 (12) | 0.0261 (9) | |
H37 | 0.673644 | 1.095191 | 0.341330 | 0.031* | |
N38 | 0.69040 (13) | 1.3863 (6) | 0.30507 (9) | 0.0237 (7) | |
C39 | 0.66427 (17) | 1.5398 (7) | 0.26633 (13) | 0.0246 (9) | |
N40 | 0.70192 (15) | 1.7232 (6) | 0.25521 (11) | 0.0255 (8) | |
H40A | 0.7420 (15) | 1.739 (7) | 0.2732 (11) | 0.031* | |
H40B | 0.6869 (16) | 1.812 (7) | 0.2298 (11) | 0.031* | |
C41 | 0.41770 (17) | 0.5401 (6) | 0.29382 (12) | 0.0207 (8) | |
N42 | 0.46068 (14) | 0.4170 (5) | 0.33163 (9) | 0.0221 (7) | |
C43 | 0.51471 (17) | 0.5525 (7) | 0.33720 (12) | 0.0250 (9) | |
H43 | 0.553560 | 0.513972 | 0.360808 | 0.030* | |
N44 | 0.50863 (14) | 0.7522 (6) | 0.30559 (9) | 0.0210 (7) | |
H44 | 0.5426 (14) | 0.874 (6) | 0.3016 (10) | 0.025* | |
C45 | 0.44727 (17) | 0.7472 (6) | 0.27787 (12) | 0.0191 (8) | |
N46 | 0.42015 (13) | 0.9092 (5) | 0.24124 (10) | 0.0234 (7) | |
C47 | 0.35805 (18) | 0.8503 (7) | 0.22242 (12) | 0.0290 (10) | |
H47 | 0.335728 | 0.957093 | 0.196643 | 0.035* | |
N48 | 0.32276 (13) | 0.6636 (6) | 0.23448 (9) | 0.0246 (7) | |
C49 | 0.35297 (18) | 0.5011 (7) | 0.27141 (12) | 0.0274 (9) | |
N50 | 0.31804 (15) | 0.3103 (6) | 0.28373 (11) | 0.0259 (8) | |
H50A | 0.2728 (15) | 0.300 (6) | 0.2687 (11) | 0.031* | |
H50B | 0.3333 (16) | 0.188 (7) | 0.3048 (11) | 0.031* | |
O1W | 0.33544 (12) | −0.6390 (5) | 0.59644 (9) | 0.0344 (7) | |
H1WA | 0.299361 | −0.641388 | 0.601298 | 0.052* | |
H1WB | 0.342410 | −0.800211 | 0.586976 | 0.052* | |
O2W | 0.35024 (13) | −1.1365 (5) | 0.55945 (8) | 0.0334 (7) | |
H2WA | 0.342899 | −1.300961 | 0.567556 | 0.050* | |
H2WB | 0.331270 | −1.133914 | 0.530377 | 0.050* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.022 (2) | 0.0164 (19) | 0.024 (2) | 0.0016 (16) | 0.0137 (19) | −0.0032 (17) |
C2 | 0.025 (2) | 0.0157 (19) | 0.027 (2) | −0.0014 (17) | 0.013 (2) | −0.0024 (18) |
C3 | 0.024 (2) | 0.022 (2) | 0.040 (3) | −0.0011 (18) | 0.012 (2) | −0.0014 (19) |
C4 | 0.031 (3) | 0.018 (2) | 0.058 (3) | −0.0062 (18) | 0.032 (2) | −0.011 (2) |
C5 | 0.044 (3) | 0.022 (2) | 0.034 (2) | −0.0008 (19) | 0.032 (2) | −0.0007 (19) |
C6 | 0.028 (2) | 0.024 (2) | 0.027 (2) | −0.0021 (18) | 0.014 (2) | −0.0075 (18) |
C7 | 0.018 (2) | 0.020 (2) | 0.028 (2) | 0.0004 (17) | 0.014 (2) | −0.0047 (18) |
O1 | 0.0247 (15) | 0.0207 (13) | 0.0225 (14) | −0.0043 (11) | 0.0121 (12) | −0.0001 (12) |
O2 | 0.0245 (15) | 0.0263 (14) | 0.0231 (15) | −0.0051 (12) | 0.0078 (13) | 0.0011 (12) |
O3 | 0.0272 (17) | 0.0222 (14) | 0.0361 (17) | −0.0073 (12) | 0.0082 (14) | −0.0032 (13) |
C11 | 0.024 (2) | 0.0162 (19) | 0.020 (2) | 0.0002 (17) | 0.0109 (18) | −0.0006 (16) |
C12 | 0.026 (2) | 0.024 (2) | 0.023 (2) | −0.0032 (18) | 0.011 (2) | −0.0084 (18) |
C13 | 0.036 (3) | 0.029 (2) | 0.028 (2) | −0.005 (2) | 0.021 (2) | −0.0002 (19) |
C14 | 0.049 (3) | 0.026 (2) | 0.032 (2) | −0.002 (2) | 0.023 (2) | 0.0050 (19) |
C15 | 0.044 (3) | 0.029 (2) | 0.031 (2) | 0.010 (2) | 0.020 (2) | 0.009 (2) |
C16 | 0.029 (2) | 0.026 (2) | 0.033 (2) | 0.0037 (18) | 0.019 (2) | 0.0034 (19) |
C17 | 0.029 (3) | 0.0174 (19) | 0.027 (2) | 0.0027 (18) | 0.015 (2) | −0.0058 (18) |
O11 | 0.0225 (15) | 0.0222 (14) | 0.0303 (16) | 0.0023 (12) | 0.0136 (13) | 0.0109 (12) |
O12 | 0.0237 (16) | 0.0387 (16) | 0.0327 (16) | 0.0073 (13) | 0.0120 (14) | 0.0138 (13) |
O13 | 0.0255 (16) | 0.0445 (17) | 0.0248 (16) | 0.0016 (14) | 0.0135 (14) | 0.0066 (13) |
C21 | 0.020 (2) | 0.0172 (19) | 0.019 (2) | −0.0012 (16) | 0.0050 (19) | −0.0021 (17) |
N22 | 0.030 (2) | 0.0235 (17) | 0.0232 (18) | −0.0043 (15) | 0.0102 (17) | 0.0028 (15) |
C23 | 0.024 (2) | 0.027 (2) | 0.029 (2) | −0.0030 (18) | 0.010 (2) | −0.0024 (19) |
N24 | 0.0218 (19) | 0.0213 (17) | 0.0235 (19) | 0.0015 (15) | 0.0095 (16) | 0.0039 (15) |
C25 | 0.020 (2) | 0.0157 (19) | 0.022 (2) | 0.0006 (17) | 0.0115 (19) | −0.0041 (17) |
N26 | 0.026 (2) | 0.0193 (16) | 0.0273 (19) | −0.0045 (14) | 0.0180 (17) | −0.0029 (14) |
C27 | 0.022 (2) | 0.027 (2) | 0.022 (2) | 0.0080 (18) | 0.0108 (19) | −0.0083 (18) |
N28 | 0.0164 (19) | 0.0202 (17) | 0.0213 (18) | −0.0034 (13) | 0.0075 (16) | −0.0039 (15) |
C29 | 0.025 (2) | 0.0183 (19) | 0.022 (2) | 0.0010 (17) | 0.011 (2) | −0.0052 (18) |
N30 | 0.021 (2) | 0.0227 (18) | 0.0226 (19) | −0.0054 (15) | 0.0059 (16) | −0.0010 (16) |
C31 | 0.026 (2) | 0.0191 (19) | 0.025 (2) | 0.0045 (17) | 0.012 (2) | −0.0036 (18) |
N32 | 0.0240 (19) | 0.0187 (16) | 0.0206 (18) | 0.0026 (14) | 0.0099 (16) | −0.0009 (14) |
C33 | 0.029 (2) | 0.0157 (18) | 0.024 (2) | 0.0037 (17) | 0.0115 (19) | −0.0002 (17) |
N34 | 0.019 (2) | 0.0172 (16) | 0.0265 (18) | −0.0002 (14) | 0.0118 (17) | 0.0006 (15) |
C35 | 0.025 (2) | 0.0140 (18) | 0.024 (2) | −0.0031 (17) | 0.016 (2) | −0.0039 (17) |
N36 | 0.0187 (19) | 0.0209 (16) | 0.0273 (18) | 0.0003 (14) | 0.0100 (16) | −0.0005 (15) |
C37 | 0.026 (2) | 0.026 (2) | 0.028 (2) | −0.0014 (18) | 0.012 (2) | −0.0030 (18) |
N38 | 0.0212 (19) | 0.0241 (17) | 0.0249 (18) | 0.0017 (14) | 0.0065 (16) | 0.0040 (15) |
C39 | 0.023 (2) | 0.022 (2) | 0.035 (3) | −0.0028 (17) | 0.014 (2) | −0.0119 (19) |
N40 | 0.0187 (19) | 0.0296 (19) | 0.029 (2) | −0.0100 (16) | 0.0096 (17) | 0.0000 (16) |
C41 | 0.022 (2) | 0.021 (2) | 0.022 (2) | 0.0002 (17) | 0.011 (2) | −0.0074 (17) |
N42 | 0.0262 (19) | 0.0214 (16) | 0.0224 (18) | 0.0051 (15) | 0.0131 (16) | 0.0041 (15) |
C43 | 0.027 (2) | 0.025 (2) | 0.027 (2) | 0.0015 (18) | 0.014 (2) | −0.0029 (18) |
N44 | 0.024 (2) | 0.0185 (16) | 0.0248 (18) | −0.0023 (14) | 0.0133 (17) | 0.0036 (15) |
C45 | 0.025 (2) | 0.0152 (19) | 0.023 (2) | −0.0002 (17) | 0.015 (2) | −0.0007 (17) |
N46 | 0.0144 (18) | 0.0263 (17) | 0.029 (2) | 0.0022 (14) | 0.0071 (16) | −0.0058 (16) |
C47 | 0.033 (3) | 0.025 (2) | 0.032 (2) | 0.0093 (19) | 0.014 (2) | −0.0016 (19) |
N48 | 0.0231 (19) | 0.0261 (17) | 0.0259 (19) | 0.0006 (15) | 0.0101 (16) | 0.0001 (15) |
C49 | 0.033 (3) | 0.024 (2) | 0.030 (2) | −0.0047 (19) | 0.017 (2) | −0.017 (2) |
N50 | 0.0227 (19) | 0.0220 (18) | 0.034 (2) | −0.0059 (16) | 0.0114 (18) | −0.0021 (15) |
O1W | 0.0331 (18) | 0.0332 (15) | 0.0432 (18) | −0.0024 (13) | 0.0213 (15) | −0.0044 (14) |
O2W | 0.0399 (18) | 0.0342 (15) | 0.0256 (15) | −0.0075 (14) | 0.0105 (15) | 0.0024 (13) |
Geometric parameters (Å, º) top
C1—C2 | 1.384 (4) | C27—H27 | 0.9500 |
C1—C6 | 1.403 (4) | N28—C29 | 1.369 (4) |
C1—C7 | 1.489 (4) | N28—H28 | 0.91 (3) |
C2—O3 | 1.374 (4) | C29—N30 | 1.320 (4) |
C2—C3 | 1.394 (4) | N30—H30A | 0.90 (3) |
C3—C4 | 1.373 (5) | N30—H30B | 0.88 (3) |
C3—H3 | 0.9500 | C31—C39 | 1.386 (5) |
C4—C5 | 1.389 (5) | C31—C35 | 1.389 (4) |
C4—H4 | 0.9500 | C31—N32 | 1.391 (4) |
C5—C6 | 1.390 (4) | N32—C33 | 1.328 (4) |
C5—H5 | 0.9500 | C33—N34 | 1.355 (4) |
C6—H6 | 0.9500 | C33—H33 | 0.9500 |
C7—O2 | 1.254 (4) | N34—C35 | 1.354 (4) |
C7—O1 | 1.286 (4) | N34—H34 | 0.95 (3) |
O3—H3A | 0.89 (3) | C35—N36 | 1.356 (4) |
C11—C16 | 1.397 (4) | N36—C37 | 1.337 (4) |
C11—C12 | 1.408 (4) | C37—N38 | 1.325 (4) |
C11—C17 | 1.477 (4) | C37—H37 | 0.9500 |
C12—O13 | 1.363 (4) | N38—C39 | 1.380 (4) |
C12—C13 | 1.397 (4) | C39—N40 | 1.350 (4) |
C13—C14 | 1.360 (5) | N40—H40A | 0.88 (3) |
C13—H13 | 0.9500 | N40—H40B | 0.87 (3) |
C14—C15 | 1.400 (4) | C41—N42 | 1.386 (4) |
C14—H14 | 0.9500 | C41—C45 | 1.388 (4) |
C15—C16 | 1.376 (4) | C41—C49 | 1.389 (5) |
C15—H15 | 0.9500 | N42—C43 | 1.332 (4) |
C16—H16 | 0.9500 | C43—N44 | 1.363 (4) |
C17—O12 | 1.229 (4) | C43—H43 | 0.9500 |
C17—O11 | 1.310 (4) | N44—C45 | 1.351 (4) |
O11—H11 | 0.89 (3) | N44—H44 | 1.00 (3) |
O13—H13A | 0.91 (3) | C45—N46 | 1.358 (4) |
C21—N22 | 1.372 (4) | N46—C47 | 1.340 (4) |
C21—C25 | 1.387 (4) | C47—N48 | 1.338 (4) |
C21—C29 | 1.401 (4) | C47—H47 | 0.9500 |
N22—C23 | 1.331 (4) | N48—C49 | 1.378 (4) |
C23—N24 | 1.361 (4) | C49—N50 | 1.350 (4) |
C23—H23 | 0.9500 | N50—H50A | 0.96 (3) |
N24—C25 | 1.349 (4) | N50—H50B | 0.87 (3) |
N24—H24 | 0.96 (3) | O1W—H1WA | 0.8701 |
C25—N26 | 1.354 (4) | O1W—H1WB | 0.8700 |
N26—C27 | 1.319 (4) | O2W—H2WA | 0.8701 |
C27—N28 | 1.358 (4) | O2W—H2WB | 0.8701 |
| | | |
C2—C1—C6 | 118.2 (3) | N28—C27—H27 | 117.3 |
C2—C1—C7 | 121.6 (3) | C27—N28—C29 | 123.2 (3) |
C6—C1—C7 | 120.1 (3) | C27—N28—H28 | 118 (2) |
O3—C2—C1 | 122.7 (3) | C29—N28—H28 | 119 (2) |
O3—C2—C3 | 115.9 (3) | N30—C29—N28 | 120.0 (3) |
C1—C2—C3 | 121.4 (3) | N30—C29—C21 | 125.4 (3) |
C4—C3—C2 | 119.1 (4) | N28—C29—C21 | 114.6 (3) |
C4—C3—H3 | 120.5 | C29—N30—H30A | 118 (2) |
C2—C3—H3 | 120.5 | C29—N30—H30B | 119 (2) |
C3—C4—C5 | 121.6 (3) | H30A—N30—H30B | 123 (3) |
C3—C4—H4 | 119.2 | C39—C31—C35 | 117.3 (3) |
C5—C4—H4 | 119.2 | C39—C31—N32 | 132.9 (3) |
C4—C5—C6 | 118.6 (3) | C35—C31—N32 | 109.8 (3) |
C4—C5—H5 | 120.7 | C33—N32—C31 | 103.9 (3) |
C6—C5—H5 | 120.7 | N32—C33—N34 | 112.8 (3) |
C5—C6—C1 | 121.2 (4) | N32—C33—H33 | 123.6 |
C5—C6—H6 | 119.4 | N34—C33—H33 | 123.6 |
C1—C6—H6 | 119.4 | C33—N34—C35 | 107.4 (3) |
O2—C7—O1 | 123.4 (3) | C33—N34—H34 | 118.9 (19) |
O2—C7—C1 | 120.2 (3) | C35—N34—H34 | 133.7 (19) |
O1—C7—C1 | 116.4 (3) | N34—C35—N36 | 128.1 (3) |
C2—O3—H3A | 107 (2) | N34—C35—C31 | 106.0 (3) |
C16—C11—C12 | 118.7 (3) | N36—C35—C31 | 125.8 (3) |
C16—C11—C17 | 121.4 (3) | C37—N36—C35 | 111.3 (3) |
C12—C11—C17 | 119.8 (3) | N38—C37—N36 | 129.4 (3) |
O13—C12—C13 | 117.4 (3) | N38—C37—H37 | 115.3 |
O13—C12—C11 | 123.0 (3) | N36—C37—H37 | 115.3 |
C13—C12—C11 | 119.6 (3) | C37—N38—C39 | 117.7 (3) |
C14—C13—C12 | 120.5 (3) | N40—C39—N38 | 118.2 (3) |
C14—C13—H13 | 119.7 | N40—C39—C31 | 123.3 (4) |
C12—C13—H13 | 119.7 | N38—C39—C31 | 118.4 (3) |
C13—C14—C15 | 120.6 (3) | C39—N40—H40A | 118 (2) |
C13—C14—H14 | 119.7 | C39—N40—H40B | 119 (2) |
C15—C14—H14 | 119.7 | H40A—N40—H40B | 122 (3) |
C16—C15—C14 | 119.6 (4) | N42—C41—C45 | 110.4 (3) |
C16—C15—H15 | 120.2 | N42—C41—C49 | 132.5 (3) |
C14—C15—H15 | 120.2 | C45—C41—C49 | 117.1 (3) |
C15—C16—C11 | 120.9 (3) | C43—N42—C41 | 103.4 (3) |
C15—C16—H16 | 119.5 | N42—C43—N44 | 113.2 (3) |
C11—C16—H16 | 119.5 | N42—C43—H43 | 123.4 |
O12—C17—O11 | 123.3 (3) | N44—C43—H43 | 123.4 |
O12—C17—C11 | 121.7 (3) | C45—N44—C43 | 106.7 (3) |
O11—C17—C11 | 115.0 (3) | C45—N44—H44 | 124.9 (17) |
C17—O11—H11 | 110 (2) | C43—N44—H44 | 128.3 (18) |
C12—O13—H13A | 118 (2) | N44—C45—N46 | 126.9 (3) |
N22—C21—C25 | 111.6 (3) | N44—C45—C41 | 106.3 (3) |
N22—C21—C29 | 131.2 (3) | N46—C45—C41 | 126.8 (3) |
C25—C21—C29 | 117.2 (3) | C47—N46—C45 | 110.4 (3) |
C23—N22—C21 | 102.8 (3) | N48—C47—N46 | 129.7 (3) |
N22—C23—N24 | 113.4 (3) | N48—C47—H47 | 115.1 |
N22—C23—H23 | 123.3 | N46—C47—H47 | 115.1 |
N24—C23—H23 | 123.3 | C47—N48—C49 | 117.5 (3) |
C25—N24—C23 | 106.9 (3) | N50—C49—N48 | 118.1 (3) |
C25—N24—H24 | 126.2 (19) | N50—C49—C41 | 123.4 (4) |
C23—N24—H24 | 126.9 (19) | N48—C49—C41 | 118.5 (3) |
N24—C25—N26 | 126.3 (3) | C49—N50—H50A | 120.6 (19) |
N24—C25—C21 | 105.4 (3) | C49—N50—H50B | 125 (2) |
N26—C25—C21 | 128.3 (3) | H50A—N50—H50B | 114 (3) |
C27—N26—C25 | 111.4 (3) | H1WA—O1W—H1WB | 109.5 |
N26—C27—N28 | 125.3 (3) | H2WA—O2W—H2WB | 104.5 |
N26—C27—H27 | 117.3 | | |
| | | |
C6—C1—C2—O3 | −176.8 (3) | C27—N28—C29—C21 | −2.8 (4) |
C7—C1—C2—O3 | 1.4 (5) | N22—C21—C29—N30 | 1.8 (6) |
C6—C1—C2—C3 | 2.5 (5) | C25—C21—C29—N30 | −179.4 (3) |
C7—C1—C2—C3 | −179.3 (3) | N22—C21—C29—N28 | −177.4 (3) |
O3—C2—C3—C4 | 178.5 (3) | C25—C21—C29—N28 | 1.4 (4) |
C1—C2—C3—C4 | −0.9 (5) | C39—C31—N32—C33 | −178.7 (4) |
C2—C3—C4—C5 | −1.0 (5) | C35—C31—N32—C33 | 0.1 (3) |
C3—C4—C5—C6 | 1.2 (5) | C31—N32—C33—N34 | −0.4 (3) |
C4—C5—C6—C1 | 0.5 (5) | N32—C33—N34—C35 | 0.6 (4) |
C2—C1—C6—C5 | −2.3 (5) | C33—N34—C35—N36 | 177.4 (3) |
C7—C1—C6—C5 | 179.5 (3) | C33—N34—C35—C31 | −0.5 (3) |
C2—C1—C7—O2 | −176.7 (3) | C39—C31—C35—N34 | 179.3 (3) |
C6—C1—C7—O2 | 1.5 (5) | N32—C31—C35—N34 | 0.3 (4) |
C2—C1—C7—O1 | 2.8 (4) | C39—C31—C35—N36 | 1.3 (5) |
C6—C1—C7—O1 | −179.0 (3) | N32—C31—C35—N36 | −177.7 (3) |
C16—C11—C12—O13 | −177.2 (3) | N34—C35—N36—C37 | −177.0 (3) |
C17—C11—C12—O13 | 3.9 (5) | C31—C35—N36—C37 | 0.5 (4) |
C16—C11—C12—C13 | 1.0 (5) | C35—N36—C37—N38 | −0.6 (5) |
C17—C11—C12—C13 | −178.0 (3) | N36—C37—N38—C39 | −1.1 (5) |
O13—C12—C13—C14 | 178.2 (3) | C37—N38—C39—N40 | −177.3 (3) |
C11—C12—C13—C14 | 0.0 (5) | C37—N38—C39—C31 | 2.9 (4) |
C12—C13—C14—C15 | −0.6 (5) | C35—C31—C39—N40 | 177.2 (3) |
C13—C14—C15—C16 | 0.3 (5) | N32—C31—C39—N40 | −4.1 (6) |
C14—C15—C16—C11 | 0.7 (5) | C35—C31—C39—N38 | −3.0 (4) |
C12—C11—C16—C15 | −1.3 (5) | N32—C31—C39—N38 | 175.7 (3) |
C17—C11—C16—C15 | 177.7 (3) | C45—C41—N42—C43 | −0.2 (3) |
C16—C11—C17—O12 | −169.9 (3) | C49—C41—N42—C43 | −177.4 (3) |
C12—C11—C17—O12 | 9.0 (5) | C41—N42—C43—N44 | 0.1 (3) |
C16—C11—C17—O11 | 9.5 (5) | N42—C43—N44—C45 | 0.1 (4) |
C12—C11—C17—O11 | −171.6 (3) | C43—N44—C45—N46 | −179.2 (3) |
C25—C21—N22—C23 | 0.6 (4) | C43—N44—C45—C41 | −0.2 (3) |
C29—C21—N22—C23 | 179.4 (3) | N42—C41—C45—N44 | 0.3 (3) |
C21—N22—C23—N24 | −0.1 (4) | C49—C41—C45—N44 | 177.9 (3) |
N22—C23—N24—C25 | −0.4 (4) | N42—C41—C45—N46 | 179.2 (3) |
C23—N24—C25—N26 | −180.0 (3) | C49—C41—C45—N46 | −3.1 (5) |
C23—N24—C25—C21 | 0.7 (3) | N44—C45—N46—C47 | −178.8 (3) |
N22—C21—C25—N24 | −0.9 (4) | C41—C45—N46—C47 | 2.5 (4) |
C29—C21—C25—N24 | −179.9 (3) | C45—N46—C47—N48 | −0.5 (5) |
N22—C21—C25—N26 | 179.9 (3) | N46—C47—N48—C49 | −0.6 (5) |
C29—C21—C25—N26 | 0.9 (5) | C47—N48—C49—N50 | −179.4 (3) |
N24—C25—N26—C27 | 179.2 (3) | C47—N48—C49—C41 | 0.0 (4) |
C21—C25—N26—C27 | −1.7 (5) | N42—C41—C49—N50 | −1.9 (6) |
C25—N26—C27—N28 | 0.2 (4) | C45—C41—C49—N50 | −178.9 (3) |
N26—C27—N28—C29 | 2.1 (5) | N42—C41—C49—N48 | 178.6 (3) |
C27—N28—C29—N30 | 178.0 (3) | C45—C41—C49—N48 | 1.6 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1 | 0.89 (3) | 1.74 (4) | 2.533 (3) | 146 (3) |
O11—H11···N32 | 0.89 (3) | 1.73 (3) | 2.608 (3) | 168 (3) |
O13—H13A···O12 | 0.91 (3) | 1.93 (3) | 2.621 (3) | 131 (3) |
O13—H13A···N38i | 0.91 (3) | 2.29 (4) | 3.000 (4) | 135 (3) |
C23—H23···O2Wii | 0.95 | 2.34 | 3.240 (4) | 158 |
N24—H24···N42 | 0.96 (3) | 1.78 (3) | 2.739 (4) | 178 (3) |
N28—H28···O1 | 0.91 (3) | 1.78 (3) | 2.683 (3) | 180 (4) |
N30—H30A···O2 | 0.90 (3) | 1.87 (3) | 2.766 (4) | 179 (3) |
N30—H30B···N22ii | 0.88 (3) | 2.04 (3) | 2.897 (4) | 164 (3) |
C33—H33···O3iii | 0.95 | 2.40 | 3.132 (4) | 134 |
N34—H34···N46 | 0.95 (3) | 1.98 (3) | 2.879 (4) | 155 (3) |
N40—H40A···O12iv | 0.88 (3) | 2.41 (3) | 3.191 (4) | 148 (3) |
N40—H40B···O12 | 0.87 (3) | 1.99 (3) | 2.856 (4) | 171 (3) |
C43—H43···O1Wv | 0.95 | 2.46 | 3.314 (5) | 150 |
N44—H44···N36 | 1.00 (3) | 1.78 (3) | 2.775 (4) | 170 (3) |
N50—H50A···N48vi | 0.96 (3) | 2.20 (3) | 3.081 (4) | 152 (3) |
N50—H50B···N26 | 0.87 (3) | 2.22 (3) | 3.071 (4) | 167 (3) |
O1W—H1WA···O13vii | 0.87 | 2.07 | 2.909 (3) | 162 |
O1W—H1WB···O2W | 0.87 | 1.88 | 2.749 (3) | 173 |
O2W—H2WA···O1Wviii | 0.87 | 1.91 | 2.770 (3) | 169 |
O2W—H2WB···O2 | 0.87 | 1.90 | 2.743 (3) | 164 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y−1, −z+1; (iii) −x+1/2, y+5/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y, −z+1; (vi) −x+1/2, y−1/2, −z+1/2; (vii) x−1/2, −y+3/2, z+1/2; (viii) x, y−1, z. |
Internal angles (°) at the N atoms of adeninium and neutral adenine, and bond
lengths (Å) of the C—O bonds of salicylate and salicylic acid topN atom | Angle' | | C—O bond | |
Compound I | | | | |
N22 | C21—N22—C23 | 121.7 (3) | C1—C7 | 1.488 (4) |
N32 | C31—N32—C33 | 123.7 (3) | C7—O1 | 1.266 (3) |
N26 | C25—N26—C27 | 105.9 (2) | C7—O2 | 1.282 (3) |
N36 | C35—N36—C37 | 107.1 (2) | C11—C17 | 1.498 (4) |
N24 | C23—N24—C25 | 110.7 (2) | C17—O11 | 1.267 (3) |
N34 | C33—N34—C35 | 112.2 (2) | C17—O12 | 1.274 (3) |
N28 | C27—N28—C29 | 103.1 (2) | | |
N38 | C37—N38—C39 | 103.5 (2) | | |
| | | | |
Compound II | | | | |
N24 | C23—N24—C25 | 106.9 (3) | C1-C7 | 1.489 (4) |
N28 | C27—N28—C29 | 123.2 (3) | C7-O2 | 1.254 (4) |
N34 | C33—N34—C35 | 107.4 (3) | C7-O1 | 1.286 (4) |
N44 | C43—N44—C45 | 106.7 (3) | C11-C17 | 1.477 (4) |
N22 | C21—N22—C23 | 102.8 (3) | C17-O12 | 1.229 (4) |
N26 | C25—N26—C27 | 111.4 (3) | C17-O11 | 1.310 (4) |
N32 | C31—N32—C33 | 103.9 (3) | | |
N36 | C35—N36—C37 | 111.3 (3) | | |
N42 | C41—N42—C43 | 103.4 (3) | | |
N46 | C45—N46—C47 | 110.4 (3) | | |