In the title compounds, C
5H
6N
5+·C
8H
7O
2−·C
8H
8O
2·H
2O, (I), and C
5H
6N
5+·C
4H
3O
4−·H
2O, (II), the adeninium cations form N—H
O hydrogen bonds with their anion counterparts and adeninium–adeninium self-association base pairs with the
R22(10) motif (Bernstein
et al., 1995). A complete hydrogen-bonding motif analysis is presented. Conventional hydrogen bonds lead to layer structures in (I) and to two-dimensional infinite polymeric ribbons in (II). C—H
O interactions are found in both structures, while weak π–π stacking interactions are only observed in (I).
Supporting information
CCDC references: 643416; 643417
To obtain crystals of (I) suitable for X-ray study, adenine (0.135 g, 1 mmol)
and phenylacetic acid (0.136 g, 2 mmol) were dissolved in water (10 ml) and
the solution was allowed to evaporate slowly. Crystals of (II) were obtained
by the slow evaporation of an equimolar solution of adenine (0.135 g) and
succinic acid (0.118 g) in what solvent? (Volume?).
All N-bound H atoms, O-bound H atoms and H atoms of the water molecules were
located in a difference Fourier map and their positions and isotropic
displacement parameters were refined. In compound (II), the N1—H1N and
O3—H3O distances were restrained with set values of 0.89 (1) and 0.86 (1) Å,
respectively. Distance restraints were also applied to O1W—H1W
and H1W···H2W of the water molecule [Please give
details]. All other H atoms were located in a difference density map, but
were positioned geometrically and included as riding atoms, with C—H
distances in the range 0.93–0.98 Å, and with Uiso(H) =
1.2Ueq(C).
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97.
(I) adeninium phenylacetate phenylacetic acid monohydrate
top
Crystal data top
C5H6N5+·C8H7O2−·C8H8O2·H2O | Z = 2 |
Mr = 425.44 | F(000) = 448 |
Triclinic, P1 | Dx = 1.334 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.7805 (10) Å | Cell parameters from 3510 reflections |
b = 10.303 (2) Å | θ = 2.2–27.6° |
c = 21.678 (5) Å | µ = 0.10 mm−1 |
α = 88.886 (4)° | T = 294 K |
β = 87.595 (3)° | Block, colourless |
γ = 83.239 (4)° | 0.22 × 0.18 × 0.12 mm |
V = 1059.2 (4) Å3 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2786 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 0.9° |
ω scans | h = −5→5 |
8134 measured reflections | k = −12→12 |
3687 independent reflections | l = −25→25 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0779P)2 + 0.0529P] where P = (Fo2 + 2Fc2)/3 |
3687 reflections | (Δ/σ)max < 0.001 |
308 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
Crystal data top
C5H6N5+·C8H7O2−·C8H8O2·H2O | γ = 83.239 (4)° |
Mr = 425.44 | V = 1059.2 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.7805 (10) Å | Mo Kα radiation |
b = 10.303 (2) Å | µ = 0.10 mm−1 |
c = 21.678 (5) Å | T = 294 K |
α = 88.886 (4)° | 0.22 × 0.18 × 0.12 mm |
β = 87.595 (3)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2786 reflections with I > 2σ(I) |
8134 measured reflections | Rint = 0.024 |
3687 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.22 e Å−3 |
3687 reflections | Δρmin = −0.14 e Å−3 |
308 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 0.1978 (4) | 0.84570 (18) | 0.53774 (8) | 0.0404 (4) | |
H2 | 0.0397 | 0.8924 | 0.5565 | 0.048* | |
C4 | 0.5233 (3) | 0.81580 (16) | 0.46291 (8) | 0.0340 (4) | |
C5 | 0.6519 (3) | 0.70216 (16) | 0.48834 (8) | 0.0334 (4) | |
C6 | 0.5405 (4) | 0.65705 (17) | 0.54456 (8) | 0.0352 (4) | |
C8 | 0.8818 (4) | 0.73358 (18) | 0.40576 (8) | 0.0406 (4) | |
H8 | 1.0143 | 0.7243 | 0.3730 | 0.049* | |
N1 | 0.3097 (3) | 0.73484 (14) | 0.56691 (7) | 0.0389 (4) | |
H1N | 0.230 (4) | 0.711 (2) | 0.6024 (10) | 0.052 (6)* | |
N3 | 0.2929 (3) | 0.89189 (14) | 0.48590 (7) | 0.0397 (4) | |
N7 | 0.8795 (3) | 0.64993 (14) | 0.45204 (7) | 0.0384 (4) | |
N9 | 0.6749 (3) | 0.83439 (15) | 0.40990 (7) | 0.0387 (4) | |
H9N | 0.658 (4) | 0.897 (2) | 0.3838 (9) | 0.044 (5)* | |
N10 | 0.6421 (4) | 0.55135 (16) | 0.57442 (8) | 0.0444 (4) | |
H10A | 0.557 (4) | 0.5283 (19) | 0.6078 (10) | 0.047 (6)* | |
H10B | 0.795 (5) | 0.5054 (19) | 0.5585 (9) | 0.043 (5)* | |
C11 | −0.0881 (4) | 0.7188 (2) | 0.69754 (8) | 0.0424 (4) | |
C12 | −0.2588 (4) | 0.6857 (2) | 0.75502 (9) | 0.0476 (5) | |
H12A | −0.4538 | 0.7221 | 0.7511 | 0.057* | |
H12B | −0.2528 | 0.5916 | 0.7594 | 0.057* | |
C13 | −0.1437 (4) | 0.73973 (19) | 0.81138 (8) | 0.0458 (5) | |
C14 | 0.0551 (5) | 0.6658 (2) | 0.84565 (10) | 0.0610 (6) | |
H14 | 0.1170 | 0.5803 | 0.8343 | 0.073* | |
C15 | 0.1623 (6) | 0.7167 (3) | 0.89623 (12) | 0.0785 (8) | |
H15 | 0.2981 | 0.6656 | 0.9184 | 0.094* | |
C16 | 0.0731 (6) | 0.8414 (3) | 0.91472 (11) | 0.0776 (8) | |
H16 | 0.1456 | 0.8751 | 0.9494 | 0.093* | |
C17 | −0.1247 (6) | 0.9157 (3) | 0.88131 (12) | 0.0778 (7) | |
H17 | −0.1867 | 1.0008 | 0.8932 | 0.093* | |
C18 | −0.2323 (5) | 0.8655 (2) | 0.83042 (11) | 0.0659 (6) | |
H18 | −0.3674 | 0.9171 | 0.8083 | 0.079* | |
O1 | −0.1423 (3) | 0.82722 (14) | 0.67209 (7) | 0.0592 (4) | |
O2 | 0.1108 (3) | 0.63633 (14) | 0.67814 (6) | 0.0526 (4) | |
C19 | 0.4626 (4) | 0.35704 (18) | 0.72295 (8) | 0.0437 (5) | |
C20 | 0.5603 (5) | 0.2422 (2) | 0.76325 (10) | 0.0629 (6) | |
H20A | 0.4712 | 0.1675 | 0.7508 | 0.075* | |
H20B | 0.7621 | 0.2210 | 0.7564 | 0.075* | |
C21 | 0.4985 (4) | 0.2629 (2) | 0.83090 (9) | 0.0526 (5) | |
C22 | 0.3188 (6) | 0.1912 (3) | 0.86351 (11) | 0.0738 (7) | |
H22 | 0.2313 | 0.1293 | 0.8432 | 0.089* | |
C23 | 0.2645 (7) | 0.2085 (4) | 0.92544 (14) | 0.0968 (10) | |
H23 | 0.1410 | 0.1583 | 0.9465 | 0.116* | |
C24 | 0.3873 (7) | 0.2971 (3) | 0.95631 (13) | 0.0894 (9) | |
H24 | 0.3493 | 0.3082 | 0.9984 | 0.107* | |
C25 | 0.5684 (7) | 0.3706 (3) | 0.92514 (14) | 0.0947 (9) | |
H25 | 0.6528 | 0.4329 | 0.9459 | 0.114* | |
C26 | 0.6264 (6) | 0.3520 (3) | 0.86221 (12) | 0.0808 (8) | |
H26 | 0.7534 | 0.4007 | 0.8413 | 0.097* | |
O3 | 0.2222 (3) | 0.42029 (17) | 0.73987 (7) | 0.0680 (5) | |
H3O | 0.182 (6) | 0.497 (3) | 0.7126 (14) | 0.105 (10)* | |
O4 | 0.5954 (3) | 0.38617 (15) | 0.67788 (6) | 0.0632 (4) | |
O1W | 0.3449 (4) | 0.97577 (15) | 0.67927 (7) | 0.0561 (4) | |
H1W | 0.506 (7) | 0.920 (3) | 0.6770 (12) | 0.090 (9)* | |
H2W | 0.206 (6) | 0.932 (3) | 0.6823 (12) | 0.090 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0352 (10) | 0.0419 (10) | 0.0432 (10) | −0.0001 (8) | −0.0016 (8) | −0.0051 (8) |
C4 | 0.0340 (9) | 0.0329 (9) | 0.0357 (9) | −0.0053 (7) | −0.0055 (7) | 0.0007 (7) |
C5 | 0.0323 (9) | 0.0339 (9) | 0.0341 (9) | −0.0025 (7) | −0.0048 (7) | −0.0002 (7) |
C6 | 0.0354 (9) | 0.0357 (9) | 0.0356 (9) | −0.0068 (7) | −0.0066 (7) | −0.0011 (7) |
C8 | 0.0406 (10) | 0.0428 (10) | 0.0369 (10) | 0.0003 (8) | 0.0011 (8) | 0.0016 (8) |
N1 | 0.0379 (8) | 0.0424 (9) | 0.0357 (8) | −0.0026 (7) | 0.0001 (7) | 0.0013 (7) |
N3 | 0.0382 (8) | 0.0365 (8) | 0.0435 (9) | −0.0003 (7) | −0.0031 (7) | 0.0005 (7) |
N7 | 0.0384 (8) | 0.0372 (8) | 0.0379 (8) | 0.0014 (6) | −0.0003 (6) | 0.0024 (6) |
N9 | 0.0445 (9) | 0.0343 (8) | 0.0362 (8) | −0.0013 (7) | −0.0029 (7) | 0.0080 (7) |
N10 | 0.0499 (10) | 0.0420 (9) | 0.0389 (9) | 0.0018 (8) | 0.0017 (8) | 0.0105 (7) |
C11 | 0.0359 (10) | 0.0513 (12) | 0.0406 (10) | −0.0076 (9) | −0.0050 (8) | 0.0047 (9) |
C12 | 0.0407 (11) | 0.0546 (12) | 0.0483 (11) | −0.0115 (9) | 0.0012 (9) | 0.0080 (9) |
C13 | 0.0404 (10) | 0.0528 (12) | 0.0438 (11) | −0.0097 (9) | 0.0096 (8) | 0.0089 (9) |
C14 | 0.0625 (14) | 0.0647 (14) | 0.0540 (13) | 0.0006 (11) | −0.0037 (11) | 0.0022 (11) |
C15 | 0.0772 (18) | 0.098 (2) | 0.0592 (15) | −0.0040 (16) | −0.0165 (13) | 0.0076 (14) |
C16 | 0.0850 (19) | 0.101 (2) | 0.0518 (14) | −0.0292 (17) | −0.0011 (13) | −0.0079 (14) |
C17 | 0.092 (2) | 0.0694 (17) | 0.0730 (17) | −0.0126 (15) | 0.0016 (15) | −0.0126 (13) |
C18 | 0.0682 (15) | 0.0618 (15) | 0.0665 (15) | −0.0023 (12) | −0.0051 (12) | 0.0022 (12) |
O1 | 0.0556 (9) | 0.0555 (9) | 0.0627 (9) | 0.0026 (7) | 0.0080 (7) | 0.0199 (7) |
O2 | 0.0498 (8) | 0.0575 (9) | 0.0465 (8) | 0.0066 (7) | 0.0035 (6) | 0.0093 (6) |
C19 | 0.0485 (11) | 0.0410 (11) | 0.0409 (11) | −0.0038 (9) | 0.0004 (9) | −0.0001 (8) |
C20 | 0.0754 (16) | 0.0509 (13) | 0.0571 (13) | 0.0092 (11) | 0.0091 (11) | 0.0106 (10) |
C21 | 0.0565 (13) | 0.0459 (11) | 0.0520 (12) | 0.0060 (10) | −0.0025 (10) | 0.0142 (9) |
C22 | 0.0819 (18) | 0.0776 (17) | 0.0627 (15) | −0.0178 (14) | 0.0096 (13) | 0.0030 (12) |
C23 | 0.100 (2) | 0.123 (3) | 0.0684 (18) | −0.026 (2) | 0.0203 (16) | 0.0091 (17) |
C24 | 0.099 (2) | 0.112 (2) | 0.0534 (15) | 0.0032 (19) | −0.0030 (15) | 0.0038 (16) |
C25 | 0.118 (3) | 0.091 (2) | 0.078 (2) | −0.0175 (19) | −0.0341 (18) | −0.0041 (16) |
C26 | 0.097 (2) | 0.0762 (18) | 0.0723 (17) | −0.0238 (15) | −0.0107 (15) | 0.0170 (14) |
O3 | 0.0602 (10) | 0.0692 (11) | 0.0671 (10) | 0.0132 (8) | 0.0166 (8) | 0.0247 (8) |
O4 | 0.0677 (10) | 0.0647 (10) | 0.0504 (9) | 0.0116 (8) | 0.0148 (7) | 0.0164 (7) |
O1W | 0.0574 (10) | 0.0455 (9) | 0.0640 (10) | −0.0034 (8) | −0.0022 (8) | 0.0164 (7) |
Geometric parameters (Å, º) top
C2—N3 | 1.297 (2) | C15—C16 | 1.368 (4) |
C2—N1 | 1.359 (2) | C15—H15 | 0.9300 |
C2—H2 | 0.9300 | C16—C17 | 1.367 (4) |
C4—N9 | 1.355 (2) | C16—H16 | 0.9300 |
C4—N3 | 1.357 (2) | C17—C18 | 1.372 (3) |
C4—C5 | 1.374 (2) | C17—H17 | 0.9300 |
C5—N7 | 1.378 (2) | C18—H18 | 0.9300 |
C5—C6 | 1.403 (2) | C19—O4 | 1.196 (2) |
C6—N10 | 1.310 (2) | C19—O3 | 1.295 (2) |
C6—N1 | 1.363 (2) | C19—C20 | 1.498 (3) |
C8—N7 | 1.310 (2) | C20—C21 | 1.498 (3) |
C8—N9 | 1.349 (2) | C20—H20A | 0.9700 |
C8—H8 | 0.9300 | C20—H20B | 0.9700 |
N1—H1N | 0.89 (2) | C21—C22 | 1.364 (3) |
N9—H9N | 0.85 (2) | C21—C26 | 1.368 (3) |
N10—H10A | 0.86 (2) | C22—C23 | 1.368 (4) |
N10—H10B | 0.89 (2) | C22—H22 | 0.9300 |
C11—O1 | 1.241 (2) | C23—C24 | 1.345 (4) |
C11—O2 | 1.262 (2) | C23—H23 | 0.9300 |
C11—C12 | 1.516 (3) | C24—C25 | 1.365 (4) |
C12—C13 | 1.503 (3) | C24—H24 | 0.9300 |
C12—H12A | 0.9700 | C25—C26 | 1.393 (4) |
C12—H12B | 0.9700 | C25—H25 | 0.9300 |
C13—C14 | 1.379 (3) | C26—H26 | 0.9300 |
C13—C18 | 1.380 (3) | O3—H3O | 0.99 (3) |
C14—C15 | 1.369 (3) | O1W—H1W | 0.91 (3) |
C14—H14 | 0.9300 | O1W—H2W | 0.85 (3) |
| | | |
N3—C2—N1 | 125.52 (17) | C16—C15—C14 | 121.1 (3) |
N3—C2—H2 | 117.2 | C16—C15—H15 | 119.5 |
N1—C2—H2 | 117.2 | C14—C15—H15 | 119.5 |
N9—C4—N3 | 127.75 (15) | C17—C16—C15 | 118.8 (3) |
N9—C4—C5 | 105.04 (15) | C17—C16—H16 | 120.6 |
N3—C4—C5 | 127.21 (15) | C15—C16—H16 | 120.6 |
C4—C5—N7 | 111.48 (15) | C16—C17—C18 | 120.5 (3) |
C4—C5—C6 | 118.34 (16) | C16—C17—H17 | 119.8 |
N7—C5—C6 | 130.17 (16) | C18—C17—H17 | 119.8 |
N10—C6—N1 | 121.34 (17) | C17—C18—C13 | 121.2 (2) |
N10—C6—C5 | 125.12 (17) | C17—C18—H18 | 119.4 |
N1—C6—C5 | 113.55 (15) | C13—C18—H18 | 119.4 |
N7—C8—N9 | 113.96 (16) | O4—C19—O3 | 122.76 (18) |
N7—C8—H8 | 123.0 | O4—C19—C20 | 122.11 (18) |
N9—C8—H8 | 123.0 | O3—C19—C20 | 115.11 (17) |
C2—N1—C6 | 123.41 (16) | C21—C20—C19 | 114.53 (18) |
C2—N1—H1N | 119.0 (14) | C21—C20—H20A | 108.6 |
C6—N1—H1N | 117.6 (14) | C19—C20—H20A | 108.6 |
C2—N3—C4 | 111.97 (15) | C21—C20—H20B | 108.6 |
C8—N7—C5 | 102.76 (15) | C19—C20—H20B | 108.6 |
C8—N9—C4 | 106.76 (15) | H20A—C20—H20B | 107.6 |
C8—N9—H9N | 123.1 (14) | C22—C21—C26 | 117.9 (2) |
C4—N9—H9N | 130.1 (13) | C22—C21—C20 | 121.2 (2) |
C6—N10—H10A | 119.5 (14) | C26—C21—C20 | 120.9 (2) |
C6—N10—H10B | 117.8 (13) | C21—C22—C23 | 121.4 (3) |
H10A—N10—H10B | 122.6 (19) | C21—C22—H22 | 119.3 |
O1—C11—O2 | 121.99 (17) | C23—C22—H22 | 119.3 |
O1—C11—C12 | 119.20 (17) | C24—C23—C22 | 120.9 (3) |
O2—C11—C12 | 118.77 (17) | C24—C23—H23 | 119.5 |
C13—C12—C11 | 110.59 (15) | C22—C23—H23 | 119.5 |
C13—C12—H12A | 109.5 | C23—C24—C25 | 119.3 (3) |
C11—C12—H12A | 109.5 | C23—C24—H24 | 120.4 |
C13—C12—H12B | 109.5 | C25—C24—H24 | 120.4 |
C11—C12—H12B | 109.5 | C24—C25—C26 | 119.9 (3) |
H12A—C12—H12B | 108.1 | C24—C25—H25 | 120.1 |
C14—C13—C18 | 117.7 (2) | C26—C25—H25 | 120.1 |
C14—C13—C12 | 121.24 (19) | C21—C26—C25 | 120.6 (3) |
C18—C13—C12 | 121.08 (19) | C21—C26—H26 | 119.7 |
C15—C14—C13 | 120.8 (2) | C25—C26—H26 | 119.7 |
C15—C14—H14 | 119.6 | C19—O3—H3O | 109.4 (18) |
C13—C14—H14 | 119.6 | H1W—O1W—H2W | 108 (3) |
| | | |
N9—C4—C5—N7 | −0.17 (19) | C11—C12—C13—C14 | −92.2 (2) |
N3—C4—C5—N7 | 179.34 (16) | C11—C12—C13—C18 | 87.4 (2) |
N9—C4—C5—C6 | 179.92 (15) | C18—C13—C14—C15 | −0.8 (3) |
N3—C4—C5—C6 | −0.6 (3) | C12—C13—C14—C15 | 178.8 (2) |
C4—C5—C6—N10 | −179.32 (16) | C13—C14—C15—C16 | 0.9 (4) |
N7—C5—C6—N10 | 0.8 (3) | C14—C15—C16—C17 | −0.6 (4) |
C4—C5—C6—N1 | 0.4 (2) | C15—C16—C17—C18 | 0.3 (4) |
N7—C5—C6—N1 | −179.49 (16) | C16—C17—C18—C13 | −0.3 (4) |
N3—C2—N1—C6 | −0.1 (3) | C14—C13—C18—C17 | 0.6 (3) |
N10—C6—N1—C2 | 179.63 (16) | C12—C13—C18—C17 | −179.1 (2) |
C5—C6—N1—C2 | −0.1 (2) | O4—C19—C20—C21 | 142.8 (2) |
N1—C2—N3—C4 | 0.0 (3) | O3—C19—C20—C21 | −38.5 (3) |
N9—C4—N3—C2 | 179.74 (17) | C19—C20—C21—C22 | 115.4 (2) |
C5—C4—N3—C2 | 0.3 (3) | C19—C20—C21—C26 | −66.2 (3) |
N9—C8—N7—C5 | 0.1 (2) | C26—C21—C22—C23 | 0.8 (4) |
C4—C5—N7—C8 | 0.04 (19) | C20—C21—C22—C23 | 179.1 (2) |
C6—C5—N7—C8 | 179.94 (18) | C21—C22—C23—C24 | 0.0 (5) |
N7—C8—N9—C4 | −0.2 (2) | C22—C23—C24—C25 | 0.0 (5) |
N3—C4—N9—C8 | −179.28 (17) | C23—C24—C25—C26 | −0.8 (5) |
C5—C4—N9—C8 | 0.22 (18) | C22—C21—C26—C25 | −1.5 (4) |
O1—C11—C12—C13 | −83.4 (2) | C20—C21—C26—C25 | −179.9 (2) |
O2—C11—C12—C13 | 94.4 (2) | C24—C25—C26—C21 | 1.6 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.89 (2) | 1.89 (2) | 2.773 (2) | 170 (2) |
N1—H1N···O1 | 0.89 (2) | 2.49 (2) | 3.156 (2) | 131.8 (17) |
N9—H9N···O1Wi | 0.85 (2) | 1.88 (2) | 2.720 (2) | 173.4 (19) |
N10—H10A···O4 | 0.86 (2) | 2.09 (2) | 2.806 (2) | 140.9 (18) |
N10—H10B···N7ii | 0.89 (2) | 2.10 (2) | 2.946 (2) | 158.6 (17) |
O3—H3O···O2 | 0.99 (3) | 1.61 (3) | 2.587 (2) | 171 (3) |
O1W—H2W···O1 | 0.85 (3) | 2.11 (3) | 2.945 (2) | 170 (3) |
O1W—H1W···O1iii | 0.91 (3) | 1.83 (3) | 2.733 (2) | 172 (3) |
C8—H8···O4ii | 0.93 | 2.32 | 3.168 (3) | 152 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x+1, y, z. |
(II) adeninium 3-carboxypropionate monohydrate
top
Crystal data top
C5H6N5+·C4H3O4−·H2O | F(000) = 560 |
Mr = 269.23 | Dx = 1.492 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8119 reflections |
a = 9.539 (3) Å | θ = 2.5–28.0° |
b = 17.149 (6) Å | µ = 0.12 mm−1 |
c = 7.450 (3) Å | T = 294 K |
β = 100.503 (5)° | Needle, colourless |
V = 1198.3 (7) Å3 | 0.25 × 0.15 × 0.07 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2112 independent reflections |
Radiation source: fine-focus sealed tube | 1934 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SABABS; Bruker, 2001) | h = −11→11 |
Tmin = 0.97, Tmax = 0.98 | k = −20→20 |
10914 measured reflections | l = −8→8 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0786P)2 + 0.1186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
2112 reflections | Δρmax = 0.21 e Å−3 |
197 parameters | Δρmin = −0.24 e Å−3 |
4 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (3) |
Crystal data top
C5H6N5+·C4H3O4−·H2O | V = 1198.3 (7) Å3 |
Mr = 269.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.539 (3) Å | µ = 0.12 mm−1 |
b = 17.149 (6) Å | T = 294 K |
c = 7.450 (3) Å | 0.25 × 0.15 × 0.07 mm |
β = 100.503 (5)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2112 independent reflections |
Absorption correction: multi-scan (SABABS; Bruker, 2001) | 1934 reflections with I > 2σ(I) |
Tmin = 0.97, Tmax = 0.98 | Rint = 0.024 |
10914 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 4 restraints |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.21 e Å−3 |
2112 reflections | Δρmin = −0.24 e Å−3 |
197 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 0.30508 (17) | 0.71386 (10) | 0.8304 (2) | 0.0553 (4) | |
H2 | 0.3819 | 0.7387 | 0.7940 | 0.066* | |
C4 | 0.09829 (16) | 0.71472 (9) | 0.92531 (18) | 0.0451 (4) | |
C5 | 0.09084 (14) | 0.63397 (8) | 0.93719 (18) | 0.0429 (3) | |
C6 | 0.20234 (15) | 0.58941 (8) | 0.88586 (18) | 0.0434 (3) | |
C8 | −0.09487 (17) | 0.67875 (9) | 1.0206 (2) | 0.0530 (4) | |
H8 | −0.1811 | 0.6823 | 1.0617 | 0.064* | |
N1 | 0.30705 (13) | 0.63444 (8) | 0.83389 (17) | 0.0506 (3) | |
H1N | 0.3853 (15) | 0.6137 (12) | 0.797 (2) | 0.073 (6)* | |
N3 | 0.20488 (15) | 0.75821 (8) | 0.87348 (19) | 0.0541 (4) | |
N7 | −0.03211 (13) | 0.61135 (7) | 0.99833 (17) | 0.0499 (3) | |
N9 | −0.02190 (14) | 0.74226 (8) | 0.97801 (19) | 0.0508 (3) | |
H9N | −0.043 (2) | 0.7913 (16) | 0.982 (3) | 0.078 (6)* | |
N10 | 0.21206 (15) | 0.51274 (7) | 0.88423 (18) | 0.0514 (3) | |
H10A | 0.292 (2) | 0.4910 (14) | 0.854 (3) | 0.081 (6)* | |
H10B | 0.139 (2) | 0.4825 (11) | 0.919 (2) | 0.061 (5)* | |
C11 | 0.56012 (16) | 0.49986 (9) | 0.7303 (2) | 0.0493 (4) | |
C12 | 0.68762 (16) | 0.46488 (9) | 0.6682 (2) | 0.0484 (4) | |
H12 | 0.6942 | 0.4109 | 0.6776 | 0.058* | |
C13 | 0.79349 (16) | 0.49941 (9) | 0.6012 (2) | 0.0487 (4) | |
H13 | 0.8625 | 0.4653 | 0.5741 | 0.058* | |
C14 | 0.81954 (16) | 0.58309 (8) | 0.5628 (2) | 0.0490 (4) | |
O1 | 0.54367 (12) | 0.57392 (7) | 0.72622 (18) | 0.0643 (4) | |
O2 | 0.47499 (13) | 0.45476 (7) | 0.78448 (17) | 0.0641 (4) | |
O3 | 0.73222 (12) | 0.63797 (6) | 0.59543 (17) | 0.0601 (3) | |
H3O | 0.6612 (18) | 0.6208 (13) | 0.646 (3) | 0.082 (6)* | |
O4 | 0.92546 (14) | 0.59986 (7) | 0.4990 (2) | 0.0721 (4) | |
O1W | 0.5899 (2) | 0.70336 (11) | 0.1990 (3) | 0.1047 (6) | |
H1W | 0.539 (4) | 0.6619 (16) | 0.155 (4) | 0.23 (2)* | |
H2W | 0.6375 | 0.7020 | 0.3096 | 0.098* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.0496 (8) | 0.0480 (9) | 0.0735 (10) | −0.0027 (7) | 0.0252 (7) | 0.0074 (7) |
C4 | 0.0428 (8) | 0.0422 (8) | 0.0521 (7) | 0.0039 (6) | 0.0133 (6) | 0.0016 (6) |
C5 | 0.0398 (7) | 0.0405 (8) | 0.0509 (7) | −0.0001 (6) | 0.0148 (5) | 0.0014 (5) |
C6 | 0.0411 (7) | 0.0414 (8) | 0.0504 (7) | 0.0008 (5) | 0.0152 (5) | 0.0012 (5) |
C8 | 0.0444 (8) | 0.0491 (9) | 0.0699 (9) | 0.0028 (6) | 0.0222 (7) | 0.0006 (7) |
N1 | 0.0447 (7) | 0.0463 (7) | 0.0664 (8) | 0.0016 (5) | 0.0250 (6) | 0.0039 (5) |
N3 | 0.0522 (7) | 0.0426 (7) | 0.0718 (8) | −0.0008 (5) | 0.0228 (6) | 0.0056 (5) |
N7 | 0.0418 (7) | 0.0453 (7) | 0.0673 (7) | 0.0007 (5) | 0.0219 (5) | 0.0010 (5) |
N9 | 0.0472 (7) | 0.0407 (7) | 0.0680 (8) | 0.0070 (5) | 0.0196 (6) | 0.0008 (5) |
N10 | 0.0475 (7) | 0.0390 (7) | 0.0733 (8) | 0.0020 (5) | 0.0263 (6) | −0.0004 (5) |
C11 | 0.0452 (8) | 0.0478 (9) | 0.0584 (8) | 0.0009 (6) | 0.0186 (6) | 0.0012 (6) |
C12 | 0.0507 (8) | 0.0354 (7) | 0.0625 (8) | 0.0043 (6) | 0.0191 (7) | 0.0022 (6) |
C13 | 0.0466 (8) | 0.0389 (7) | 0.0649 (8) | 0.0059 (6) | 0.0215 (6) | −0.0027 (6) |
C14 | 0.0464 (8) | 0.0399 (8) | 0.0649 (8) | −0.0008 (6) | 0.0211 (6) | −0.0046 (6) |
O1 | 0.0554 (7) | 0.0455 (7) | 0.1020 (9) | 0.0072 (5) | 0.0410 (6) | 0.0024 (5) |
O2 | 0.0581 (7) | 0.0524 (7) | 0.0905 (8) | −0.0028 (5) | 0.0367 (6) | 0.0046 (5) |
O3 | 0.0559 (7) | 0.0361 (6) | 0.0964 (9) | 0.0025 (5) | 0.0354 (6) | −0.0006 (5) |
O4 | 0.0662 (8) | 0.0469 (6) | 0.1172 (10) | −0.0053 (5) | 0.0541 (7) | −0.0034 (6) |
O1W | 0.0806 (11) | 0.0699 (10) | 0.1677 (17) | −0.0015 (8) | 0.0334 (10) | 0.0091 (11) |
Geometric parameters (Å, º) top
C2—N3 | 1.307 (2) | N10—H10A | 0.91 (2) |
C2—N1 | 1.362 (2) | N10—H10B | 0.943 (19) |
C2—H2 | 0.9300 | C11—O2 | 1.2410 (19) |
C4—N9 | 1.362 (2) | C11—O1 | 1.279 (2) |
C4—N3 | 1.372 (2) | C11—C12 | 1.503 (2) |
C4—C5 | 1.390 (2) | C12—C13 | 1.343 (2) |
C5—N7 | 1.3886 (18) | C12—H12 | 0.9300 |
C5—C6 | 1.418 (2) | C13—C14 | 1.493 (2) |
C6—N10 | 1.318 (2) | C13—H13 | 0.9300 |
C6—N1 | 1.3730 (19) | C14—O4 | 1.2266 (19) |
C8—N7 | 1.326 (2) | C14—O3 | 1.3087 (18) |
C8—N9 | 1.361 (2) | O3—H3O | 0.883 (10) |
C8—H8 | 0.9300 | O1W—H1W | 0.89 (3) |
N1—H1N | 0.914 (10) | O1W—H2W | 0.87 |
N9—H9N | 0.87 (3) | | |
| | | |
N3—C2—N1 | 125.83 (14) | C8—N9—C4 | 106.44 (13) |
N3—C2—H2 | 117.1 | C8—N9—H9N | 129.6 (16) |
N1—C2—H2 | 117.1 | C4—N9—H9N | 123.9 (16) |
N9—C4—N3 | 126.76 (14) | C6—N10—H10A | 118.3 (15) |
N9—C4—C5 | 105.75 (13) | C6—N10—H10B | 119.3 (12) |
N3—C4—C5 | 127.48 (13) | H10A—N10—H10B | 122.3 (19) |
N7—C5—C4 | 110.81 (12) | O2—C11—O1 | 122.79 (14) |
N7—C5—C6 | 131.15 (13) | O2—C11—C12 | 117.76 (14) |
C4—C5—C6 | 118.04 (12) | O1—C11—C12 | 119.45 (13) |
N10—C6—N1 | 120.16 (13) | C13—C12—C11 | 130.10 (14) |
N10—C6—C5 | 126.69 (13) | C13—C12—H12 | 115.0 |
N1—C6—C5 | 113.15 (13) | C11—C12—H12 | 115.0 |
N7—C8—N9 | 113.99 (14) | C12—C13—C14 | 131.14 (14) |
N7—C8—H8 | 123.0 | C12—C13—H13 | 114.4 |
N9—C8—H8 | 123.0 | C14—C13—H13 | 114.4 |
C2—N1—C6 | 124.03 (13) | O4—C14—O3 | 120.04 (14) |
C2—N1—H1N | 113.1 (14) | O4—C14—C13 | 118.51 (13) |
C6—N1—H1N | 122.9 (14) | O3—C14—C13 | 121.45 (13) |
C2—N3—C4 | 111.45 (13) | C14—O3—H3O | 113.8 (16) |
C8—N7—C5 | 103.01 (12) | H1W—O1W—H2W | 119 |
| | | |
N9—C4—C5—N7 | −0.55 (16) | C5—C4—N3—C2 | 1.1 (2) |
N3—C4—C5—N7 | 178.76 (14) | N9—C8—N7—C5 | 0.20 (18) |
N9—C4—C5—C6 | 178.68 (12) | C4—C5—N7—C8 | 0.23 (16) |
N3—C4—C5—C6 | −2.0 (2) | C6—C5—N7—C8 | −178.87 (15) |
N7—C5—C6—N10 | 0.6 (2) | N7—C8—N9—C4 | −0.55 (19) |
C4—C5—C6—N10 | −178.43 (14) | N3—C4—N9—C8 | −178.68 (14) |
N7—C5—C6—N1 | −179.49 (13) | C5—C4—N9—C8 | 0.64 (16) |
C4—C5—C6—N1 | 1.46 (18) | O2—C11—C12—C13 | 178.74 (15) |
N3—C2—N1—C6 | −0.6 (2) | O1—C11—C12—C13 | −1.5 (2) |
N10—C6—N1—C2 | 179.56 (14) | C11—C12—C13—C14 | −1.2 (3) |
C5—C6—N1—C2 | −0.3 (2) | C12—C13—C14—O4 | −179.32 (17) |
N1—C2—N3—C4 | 0.3 (2) | C12—C13—C14—O3 | 0.6 (3) |
N9—C4—N3—C2 | −179.76 (14) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1 | 0.91 (1) | 1.82 (2) | 2.734 (2) | 179 (2) |
N9—H9N···O4i | 0.87 (3) | 1.90 (3) | 2.763 (2) | 176 (2) |
N10—H10A···O2 | 0.91 (2) | 2.01 (2) | 2.917 (2) | 174 (2) |
N10—H10B···N7ii | 0.943 (19) | 2.06 (2) | 2.964 (2) | 161 (2) |
O3—H3O···O1 | 0.88 (1) | 1.58 (1) | 2.4557 (17) | 169 (2) |
O1W—H1W···O2iii | 0.89 (3) | 2.06 (2) | 2.789 (2) | 138 (2) |
O1W—H2W···O3 | 0.87 | 2.42 | 3.219 (3) | 154 |
C2—H2···O1Wiv | 0.93 | 2.44 | 3.365 (3) | 177 |
C13—H13···O4v | 0.93 | 2.46 | 3.372 (2) | 168 |
Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z+1/2; (v) −x+2, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C5H6N5+·C8H7O2−·C8H8O2·H2O | C5H6N5+·C4H3O4−·H2O |
Mr | 425.44 | 269.23 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 294 | 294 |
a, b, c (Å) | 4.7805 (10), 10.303 (2), 21.678 (5) | 9.539 (3), 17.149 (6), 7.450 (3) |
α, β, γ (°) | 88.886 (4), 87.595 (3), 83.239 (4) | 90, 100.503 (5), 90 |
V (Å3) | 1059.2 (4) | 1198.3 (7) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.12 |
Crystal size (mm) | 0.22 × 0.18 × 0.12 | 0.25 × 0.15 × 0.07 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – | Multi-scan (SABABS; Bruker, 2001) |
Tmin, Tmax | – | 0.97, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8134, 3687, 2786 | 10914, 2112, 1934 |
Rint | 0.024 | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.131, 1.05 | 0.044, 0.124, 1.16 |
No. of reflections | 3687 | 2112 |
No. of parameters | 308 | 197 |
No. of restraints | 0 | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.14 | 0.21, −0.24 |
Selected geometric parameters (Å, º) for (I) topC11—O1 | 1.241 (2) | C19—O4 | 1.196 (2) |
C11—O2 | 1.262 (2) | C19—O3 | 1.295 (2) |
| | | |
C2—N1—C6 | 123.41 (16) | O4—C19—O3 | 122.76 (18) |
O1—C11—O2 | 121.99 (17) | O4—C19—C20 | 122.11 (18) |
O1—C11—C12 | 119.20 (17) | O3—C19—C20 | 115.11 (17) |
O2—C11—C12 | 118.77 (17) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2 | 0.89 (2) | 1.89 (2) | 2.773 (2) | 170 (2) |
N1—H1N···O1 | 0.89 (2) | 2.49 (2) | 3.156 (2) | 131.8 (17) |
N9—H9N···O1Wi | 0.85 (2) | 1.88 (2) | 2.720 (2) | 173.4 (19) |
N10—H10A···O4 | 0.86 (2) | 2.09 (2) | 2.806 (2) | 140.9 (18) |
N10—H10B···N7ii | 0.89 (2) | 2.10 (2) | 2.946 (2) | 158.6 (17) |
O3—H3O···O2 | 0.99 (3) | 1.61 (3) | 2.587 (2) | 171 (3) |
O1W—H2W···O1 | 0.85 (3) | 2.11 (3) | 2.945 (2) | 170 (3) |
O1W—H1W···O1iii | 0.91 (3) | 1.83 (3) | 2.733 (2) | 172 (3) |
C8—H8···O4ii | 0.93 | 2.32 | 3.168 (3) | 152 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x+1, y, z. |
Selected geometric parameters (Å, º) for (II) topC11—O2 | 1.2410 (19) | C11—O1 | 1.279 (2) |
| | | |
C2—N1—C6 | 124.03 (13) | O4—C14—O3 | 120.04 (14) |
O2—C11—O1 | 122.79 (14) | O4—C14—C13 | 118.51 (13) |
O2—C11—C12 | 117.76 (14) | O3—C14—C13 | 121.45 (13) |
O1—C11—C12 | 119.45 (13) | | |
| | | |
C11—C12—C13—C14 | −1.2 (3) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1 | 0.914 (10) | 1.821 (16) | 2.734 (2) | 179 (2) |
N9—H9N···O4i | 0.87 (3) | 1.90 (3) | 2.763 (2) | 176 (2) |
N10—H10A···O2 | 0.91 (2) | 2.01 (2) | 2.917 (2) | 174 (2) |
N10—H10B···N7ii | 0.943 (19) | 2.06 (2) | 2.964 (2) | 161 (2) |
O3—H3O···O1 | 0.883 (10) | 1.583 (11) | 2.4557 (17) | 169 (2) |
O1W—H1W···O2iii | 0.89 (3) | 2.06 (2) | 2.789 (2) | 138 (2) |
O1W—H2W···O3 | 0.87 | 2.42 | 3.219 (3) | 154 |
C2—H2···O1Wiv | 0.93 | 2.44 | 3.365 (3) | 176.7 |
C13—H13···O4v | 0.93 | 2.46 | 3.372 (2) | 168.0 |
Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z+1/2; (v) −x+2, −y+1, −z+1. |
Protonated nucleobases are present in many biochemical processes, such as enzymatic reactions and the stabilization of triplex structures, and they play a key role in a newly emerging feature of nucleic acid chemistry, namely acid–base catalysis (Lippert, 2005). Among the nucleobases, adenine shows the widest range of binding possibilities (Salam & Aoki, 2000) because it exhibits at least five donor sites and forms a great variety of complexes. Adenine forms hydrogen bonds with other nucleobases that can lead to the formation of supramolecular structures, which can be of chemical and biological interest (Shipman et al., 2000; Bazzicalupi et al., 2001). Phenylacetic acid has been found to be an active auxin (a type of plant hormone) molecule, predominantly found in fruits and also used in penicillin G production (Hillenga et al., 1995). Succinic acid is a dicarboxylic acid which occurs naturally in plant and animal tissues and plays a significant role in intermediary metabolism (Krebs cycle) in the body. Our particular interest lies in the structure of the crystalline complexes of adenine with aromatic and dicarboxylic acids and examining the interactions between the components. Recently, we reported the crystal structure of bis(adeninium) phthalate phthalic acid 1.45-hydrate (Sridhar & Ravikumar, 2007). In the present study, the crystal structures of adeninium phenylacetate phenylacetic acid hydrate, (I), and adeninium succinate hydrate, (II), are presented
The asymmetric unit of (I) contains one adeninium cation, one phenylacetate anion, one neutral phenylacetic acid and one water molecule (Fig. 1).
Adeninium cations can be either mono- or diprotonated and the bond lengths and angles are dependent on the degree of protonation (Hingerty et al., 1981; Langer & Huml, 1978). It is well documented that the N9H amine form of adenine is the most stable in gas phase and water solution (pKa = 9.8) (Gu & Leszcynski, 1999; Perun et al., 2005). This canonical tautomeric form contains three basic N atoms. The most basic site (pKa = 4.2) is N1, which accepts the first proton; the next protonation occurs at N7, and the next at N3.
In both structures, atom N1 is protonated, which can be seen from the increase in the C2—N1—C6 bond angles (Tables 1 and 3); the corresponding value for neutral adenine is 119.8° (Voet & Rich, 1970). The location of the H atom bonded to atom N1 in the difference Fourier map and the successful refinement of this H atom confirmed the site of protonation in both structures.
The adeninium base is nearly planar and the dihedral angle between the least-squares planes through the six- and five-membered rings are 0.42 (9)° for (I) and 0.95 (8)° for (II), respectively.
The molecular geometries of phenylacetic acid in its anionic and neutral forms in (I) are in good agreement with those of a similar structure (Hodgson & Asplund, 1991). The near equality of C—O distances and O—C—C angles (Table 1) clearly shows the existence of the carboxylate group based on C11, whilst differences in the C—O distances and O—C—C angles (Table 1) confirm the carboxyl group (C19). In the phenylacetate anion, the mean plane of the carboxylate group (C11/O1/O2) is rotated from the plane of the benzene ring (C13–C18) by 71.9 (1)°, while in the neutral phenylacetic acid, the plane of the carboxyl group (C19/O3/O4) is rotated by 85.7 (1)° with respect to its attached benzene ring plane (C21–C26).
The asymmetric unit of (II) comprises one adeninium cation, one succinate anion and one water molecule, with one of the carboxyl groups in the succinic acid deprotonated (Fig. 2). The two carboxyl groups are in a cis orientation with respect to the central C—C bond (Table 3). The O—H bond of the carboxyl group is in a trans conformation with respect to the C═O bond of the carboxylate group, as evidenced from the torsion angle H3O—O3—C14—O4 = -177 (1)°. This orientation can be attributed to an intramolecular O—H···O hydrogen bond involving the carboxyl and carboxylate groups of the succinate anion, leading to the formation of an S(7) motif (Bernstein et al., 1995).
In the crystal structure of (I), there are six different modes of hydrogen-bonding interactions viz. cation–cation, cation–anion, cation–neutral, anion–neutral, cation–water and water–anion (Table 2), while in the crystal structure of (II), only four different modes of hydrogen-bonding interactions are observed, viz. cation–cation, cation–anion, anion–anion and water–anion (Table 4). The adeninium cation forms N—H···O hydrogen bonds with the phenylacetate anion, the neutral phenylacetic acid and the water molecule in (I) (Table 2), while in (II), it forms N—H···O hydrogen bonds with only the succinate anion (Table 4). In both structures, intermolecular N—H···N hydrogen bonds involving the Hoogsteen faces (atoms N10 and N7) of the adeninium cations form a centrosymmetric dimer generating a characteristic R22(10) motif (Figs. 3 and 4). In (I), the Watson–Crick edges (atoms N1 and N10) of the cation link the anion and the neutral phenylacetic acid molecule through a three-centred hydrogen-bonding pattern (Jeffrey & Saenger, 1991). The anion and neutral phenylacetic acid molecules are interconnected by a strong O—H···O hydrogen bond (entry 6, Table 2). Thus, the combination of these N—H···O and O—H···O hydrogen bonds leads to the formation of an R33(12) motif. In (II), the Watson–Crick edges of the cation link the succinate anion through N—H···O hydrogen bonds, generating an R22(8) motif (Fig 4).
The water molecule plays a dual role as both donor and acceptor in the hydrogen-bonding interactions in (I) (Table 2). It participates in three hydrogen bonds, acting as donor to an adjacent phenylacetate anion and a symmetry-related one [Symmetry code?] via O—H···O hydrogen bonds, and as an acceptor to an adeninium cation via an intermolecular N—H···O hydrogen bond. In (II), the water molecule acts only as a donor and links the two succinate anions via O—H···O hydrogen bonding.
In (I), the combination of O—H···O, N—H···O and N—H···N hydrogen bonds involving the adeninium cations, the phenylacetate anions and the neutral phenylacetic acid molecules leads to hydrogen-bonded columns, which extend parallel to the c axis. Each column consists of chains of adeninium cations sandwiched between the hydrophilic chains of phenylacetate anions and the neutral phenylacetic acid molecules. The water molecule in turn produces a hydrogen-bonded network cavity of R66(24) motif (Fig. 3) by cross-linking the columns of adeninium cations, phenylacetate anions and neutral phenylacetic acid molecules to give hydrogen-bonded layers which lie parallel to the (010) plane. The shortest distance between the atoms N3···N3i in the cavity is 3.409 (2) Å [symmetry code: (i) -x, 1 - y + 2, -z + 1 Please check symmetry code. Should it be -x + 1, -y + 2, -z + 1 ?].
In (II), the R22(10) and R22(8) motifs are arranged alternately and form hydrogen-bonded columns in the crystal packing along the c axis (Fig. 4). Each hydrogen-bonded column is further interlinked to its adjacent glide-related columns by intermolecular N—H···O hydrogen bonds (Table 4). Water molecules connect neighbouring hydrogen-bonded columns and form a rather circular-shaped hydrogen-bonded network cavity (Fig. 4), thereby generating a characteristic R44(18) motif. These hydrogen-bonded columns aggregate as infinite two-dimensional hydrogen-bonded polymeric ribbons.
It is noteworthy that in (I), the water molecule does not have any interactions with the neutral phenylacetic acid, while in (II), it links the cation only through a weak C—H···O interaction. In both structures, weak C—H···O interactions are observed in the crystal packing. In (I), possible weak π–π stacking interactions exist between the aromatic rings of the adeninium base, with the distance between the centroids of the rings defined by atoms C4/C5/N7/C8/N9 and atoms N1/C2/N3/C4/C5/C6 at (x + 1, y, z) being 3.768 (1) Å, the interplanar spacing being 3.259 (1) Å and the centroid offset being 1.89 Å. No such π–π stacking interaction is observed in (II).