Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102022333/fr1405sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102022333/fr1405Isup2.hkl |
CCDC reference: 204055
The title compound was prepared by mixing 2-aminopyridine and benzoic acid in a 1:1 molar ratio in ethanol (95%) at 353 K, and crystals of (I) were obtained by slow evaporation of the solvent.
C—H distances were refined in the range 0.950 (13)–0.997 (13) Å, and Uiso values for H atoms are in the range 0.041 (3)–0.066 (5) Å2.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997).
C5H7N2+·C7H5O2− | Dx = 1.322 Mg m−3 |
Mr = 216.24 | Melting point: 422 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 986 reflections |
a = 12.2129 (17) Å | θ = 2.8–26.6° |
b = 11.5137 (16) Å | µ = 0.09 mm−1 |
c = 15.456 (2) Å | T = 208 K |
V = 2173.4 (5) Å3 | Prism, colourless |
Z = 8 | 0.40 × 0.30 × 0.15 mm |
F(000) = 912 |
Bruker SMART CCD area-detector diffractometer | 2650 independent reflections |
Radiation source: fine-focus sealed tube | 1664 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
ω scans | θmax = 28.8°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −16→16 |
Tmin = 0.964, Tmax = 0.986 | k = −14→14 |
13050 measured reflections | l = −12→20 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | All H-atom parameters refined |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0498P)2 |
S = 0.89 | (Δ/σ)max < 0.001 |
2650 reflections | Δρmax = 0.16 e Å−3 |
194 parameters | Δρmin = −0.17 e Å−3 |
0 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: 0.0145 (12) |
C5H7N2+·C7H5O2− | V = 2173.4 (5) Å3 |
Mr = 216.24 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.2129 (17) Å | µ = 0.09 mm−1 |
b = 11.5137 (16) Å | T = 208 K |
c = 15.456 (2) Å | 0.40 × 0.30 × 0.15 mm |
Bruker SMART CCD area-detector diffractometer | 2650 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 1664 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.986 | Rint = 0.065 |
13050 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.088 | All H-atom parameters refined |
S = 0.89 | Δρmax = 0.16 e Å−3 |
2650 reflections | Δρmin = −0.17 e Å−3 |
194 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 | ||
O1 | 0.62593 (6) | 0.44911 (7) | 0.43041 (5) | 0.0395 (2) | |
O2 | 0.59058 (6) | 0.62265 (7) | 0.37343 (6) | 0.0434 (2) | |
N1 | 0.79645 (8) | 0.54400 (8) | 0.51018 (6) | 0.0339 (2) | |
N2 | 0.77734 (9) | 0.72376 (9) | 0.44664 (7) | 0.0454 (3) | |
C1 | 0.83142 (9) | 0.65460 (9) | 0.50104 (7) | 0.0347 (3) | |
C2 | 0.92242 (10) | 0.69101 (11) | 0.54985 (8) | 0.0403 (3) | |
C3 | 0.97307 (11) | 0.61424 (12) | 0.60330 (8) | 0.0470 (3) | |
C4 | 0.93678 (11) | 0.49911 (12) | 0.60993 (9) | 0.0469 (3) | |
C5 | 0.84824 (10) | 0.46769 (11) | 0.56311 (8) | 0.0404 (3) | |
C6 | 0.56793 (9) | 0.51828 (9) | 0.38525 (7) | 0.0318 (3) | |
C7 | 0.46694 (8) | 0.47050 (9) | 0.34263 (7) | 0.0314 (3) | |
C8 | 0.39861 (9) | 0.54416 (11) | 0.29612 (7) | 0.0383 (3) | |
C9 | 0.30646 (10) | 0.50147 (12) | 0.25465 (8) | 0.0452 (3) | |
C10 | 0.28187 (11) | 0.38443 (12) | 0.25919 (8) | 0.0468 (3) | |
C11 | 0.34884 (11) | 0.31044 (12) | 0.30488 (8) | 0.0485 (3) | |
C12 | 0.44105 (10) | 0.35311 (11) | 0.34684 (8) | 0.0414 (3) | |
H2 | 0.9492 (10) | 0.7692 (12) | 0.5447 (8) | 0.051 (4)* | |
H3 | 1.0352 (12) | 0.6391 (12) | 0.6366 (9) | 0.056 (4)* | |
H4 | 0.9739 (12) | 0.4426 (12) | 0.6463 (9) | 0.058 (4)* | |
H5 | 0.8176 (9) | 0.3896 (11) | 0.5635 (7) | 0.041 (3)* | |
H8 | 0.4200 (10) | 0.6262 (11) | 0.2927 (8) | 0.048 (3)* | |
H9 | 0.2577 (11) | 0.5554 (11) | 0.2221 (8) | 0.050 (3)* | |
H10 | 0.2168 (11) | 0.3553 (11) | 0.2308 (9) | 0.055 (4)* | |
H11 | 0.3348 (11) | 0.2293 (12) | 0.3066 (9) | 0.065 (4)* | |
H12 | 0.4882 (10) | 0.3020 (11) | 0.3794 (8) | 0.043 (3)* | |
H13 | 0.7320 (11) | 0.5165 (11) | 0.4779 (8) | 0.050 (4)* | |
H14 | 0.7146 (12) | 0.6967 (12) | 0.4178 (9) | 0.060 (4)* | |
H15 | 0.8064 (12) | 0.7968 (14) | 0.4374 (9) | 0.066 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0373 (4) | 0.0321 (4) | 0.0490 (5) | 0.0018 (3) | −0.0114 (4) | 0.0017 (4) |
O2 | 0.0378 (5) | 0.0297 (4) | 0.0626 (6) | −0.0010 (3) | −0.0045 (4) | 0.0037 (4) |
N1 | 0.0334 (5) | 0.0324 (5) | 0.0358 (6) | −0.0051 (4) | −0.0031 (4) | −0.0019 (4) |
N2 | 0.0464 (6) | 0.0316 (6) | 0.0582 (7) | −0.0067 (5) | −0.0083 (5) | 0.0045 (5) |
C1 | 0.0351 (6) | 0.0332 (6) | 0.0358 (6) | −0.0033 (5) | 0.0054 (5) | −0.0055 (5) |
C2 | 0.0388 (6) | 0.0419 (7) | 0.0402 (7) | −0.0097 (5) | 0.0032 (6) | −0.0086 (6) |
C3 | 0.0389 (7) | 0.0624 (9) | 0.0396 (7) | −0.0080 (6) | −0.0046 (6) | −0.0111 (6) |
C4 | 0.0473 (7) | 0.0530 (8) | 0.0406 (7) | 0.0000 (6) | −0.0086 (6) | 0.0005 (6) |
C5 | 0.0454 (7) | 0.0383 (7) | 0.0375 (7) | −0.0021 (6) | −0.0022 (6) | 0.0012 (5) |
C6 | 0.0291 (6) | 0.0324 (6) | 0.0339 (6) | 0.0031 (5) | 0.0044 (5) | −0.0021 (5) |
C7 | 0.0292 (5) | 0.0365 (6) | 0.0285 (6) | 0.0012 (5) | 0.0032 (5) | −0.0009 (5) |
C8 | 0.0379 (6) | 0.0413 (7) | 0.0356 (7) | 0.0065 (5) | 0.0011 (5) | −0.0010 (5) |
C9 | 0.0393 (7) | 0.0575 (9) | 0.0387 (7) | 0.0100 (6) | −0.0074 (6) | −0.0041 (6) |
C10 | 0.0381 (7) | 0.0660 (9) | 0.0364 (7) | −0.0064 (6) | −0.0057 (6) | −0.0060 (6) |
C11 | 0.0538 (8) | 0.0486 (8) | 0.0430 (8) | −0.0147 (6) | −0.0071 (6) | 0.0021 (6) |
C12 | 0.0442 (7) | 0.0407 (7) | 0.0391 (7) | −0.0046 (6) | −0.0080 (6) | 0.0046 (6) |
O1—C6 | 1.2740 (13) | C4—H4 | 0.973 (15) |
O2—C6 | 1.2466 (13) | C5—H5 | 0.974 (12) |
N1—C1 | 1.3505 (14) | C6—C7 | 1.5027 (15) |
N1—C5 | 1.3570 (15) | C7—C12 | 1.3896 (16) |
N1—H13 | 0.985 (14) | C7—C8 | 1.3902 (15) |
N2—C1 | 1.3332 (15) | C8—C9 | 1.3853 (17) |
N2—H14 | 0.940 (15) | C8—H8 | 0.982 (12) |
N2—H15 | 0.924 (16) | C9—C10 | 1.3824 (19) |
C1—C2 | 1.4071 (16) | C9—H9 | 0.997 (13) |
C2—C3 | 1.3589 (19) | C10—C11 | 1.3761 (19) |
C2—H2 | 0.961 (14) | C10—H10 | 0.968 (13) |
C3—C4 | 1.4014 (19) | C11—C12 | 1.3893 (18) |
C3—H3 | 0.961 (14) | C11—H11 | 0.950 (13) |
C4—C5 | 1.3505 (18) | C12—H12 | 0.964 (13) |
C1—N1—C5 | 121.74 (10) | O2—C6—O1 | 124.02 (10) |
C1—N1—H13 | 120.2 (8) | O2—C6—C7 | 118.09 (10) |
C5—N1—H13 | 118.0 (8) | O1—C6—C7 | 117.88 (10) |
C1—N2—H14 | 120.3 (9) | C12—C7—C8 | 118.76 (10) |
C1—N2—H15 | 116.8 (9) | C12—C7—C6 | 121.49 (10) |
H14—N2—H15 | 122.9 (12) | C8—C7—C6 | 119.74 (10) |
N2—C1—N1 | 118.19 (10) | C9—C8—C7 | 120.70 (12) |
N2—C1—C2 | 123.47 (11) | C9—C8—H8 | 122.2 (7) |
N1—C1—C2 | 118.34 (11) | C7—C8—H8 | 117.0 (7) |
C3—C2—C1 | 119.45 (12) | C10—C9—C8 | 119.92 (12) |
C3—C2—H2 | 120.3 (8) | C10—C9—H9 | 120.2 (7) |
C1—C2—H2 | 120.2 (8) | C8—C9—H9 | 119.9 (7) |
C2—C3—C4 | 121.04 (12) | C11—C10—C9 | 120.03 (12) |
C2—C3—H3 | 119.4 (8) | C11—C10—H10 | 120.4 (8) |
C4—C3—H3 | 119.5 (8) | C9—C10—H10 | 119.6 (8) |
C5—C4—C3 | 117.87 (13) | C10—C11—C12 | 120.17 (13) |
C5—C4—H4 | 120.3 (8) | C10—C11—H11 | 121.1 (9) |
C3—C4—H4 | 121.8 (8) | C12—C11—H11 | 118.7 (9) |
C4—C5—N1 | 121.52 (12) | C11—C12—C7 | 120.43 (12) |
C4—C5—H5 | 123.5 (7) | C11—C12—H12 | 120.7 (7) |
N1—C5—H5 | 115.0 (7) | C7—C12—H12 | 118.8 (7) |
C5—N1—C1—N2 | 178.83 (11) | O2—C6—C7—C8 | −3.84 (16) |
C5—N1—C1—C2 | −1.63 (16) | O1—C6—C7—C8 | 177.02 (10) |
N2—C1—C2—C3 | −179.53 (12) | C12—C7—C8—C9 | −0.05 (17) |
N1—C1—C2—C3 | 0.96 (16) | C6—C7—C8—C9 | 178.49 (10) |
C1—C2—C3—C4 | 0.64 (19) | C7—C8—C9—C10 | −0.12 (18) |
C2—C3—C4—C5 | −1.6 (2) | C8—C9—C10—C11 | 0.02 (19) |
C3—C4—C5—N1 | 0.95 (19) | C9—C10—C11—C12 | 0.3 (2) |
C1—N1—C5—C4 | 0.67 (18) | C10—C11—C12—C7 | −0.4 (2) |
O2—C6—C7—C12 | 174.66 (10) | C8—C7—C12—C11 | 0.33 (17) |
O1—C6—C7—C12 | −4.48 (16) | C6—C7—C12—C11 | −178.19 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H13···O1 | 0.985 (14) | 1.678 (14) | 2.6552 (12) | 170.9 (12) |
N2—H14···O2 | 0.940 (15) | 1.868 (16) | 2.7996 (14) | 170.6 (13) |
N2—H15···O1i | 0.924 (16) | 1.942 (16) | 2.8619 (14) | 173.9 (13) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C5H7N2+·C7H5O2− |
Mr | 216.24 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 208 |
a, b, c (Å) | 12.2129 (17), 11.5137 (16), 15.456 (2) |
V (Å3) | 2173.4 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.30 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.964, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13050, 2650, 1664 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.677 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.088, 0.89 |
No. of reflections | 2650 |
No. of parameters | 194 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1997).
O1—C6 | 1.2740 (13) | N1—H13 | 0.985 (14) |
O2—C6 | 1.2466 (13) | N2—C1 | 1.3332 (15) |
N1—C1 | 1.3505 (14) | N2—H14 | 0.940 (15) |
N1—C5 | 1.3570 (15) | N2—H15 | 0.924 (16) |
C1—N1—C5 | 121.74 (10) | H14—N2—H15 | 122.9 (12) |
C1—N1—H13 | 120.2 (8) | O2—C6—O1 | 124.02 (10) |
C5—N1—H13 | 118.0 (8) | O2—C6—C7 | 118.09 (10) |
C1—N2—H14 | 120.3 (9) | O1—C6—C7 | 117.88 (10) |
C1—N2—H15 | 116.8 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H13···O1 | 0.985 (14) | 1.678 (14) | 2.6552 (12) | 170.9 (12) |
N2—H14···O2 | 0.940 (15) | 1.868 (16) | 2.7996 (14) | 170.6 (13) |
N2—H15···O1i | 0.924 (16) | 1.942 (16) | 2.8619 (14) | 173.9 (13) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
The present work is part of a structural study of complexes of 2-aminopyridinium systems with hydrogen-bond donors, and we report here on the structure of 2-aminopyridinium benzoate, (I). A similar series of complexes formed from 2-aminopyridine and carboxylates has been reported previously (Büyükgüngör & Odabaşoǧlu, 2002; Odabaşoǧlu et al., 2002). Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997) and crystal-engineering research (Goswami et al., 1998). The design of highly specific solid-state structures is of considerable significance in organic chemistry, due to their important applications in the development of new optical, magnetic and electronic systems (Ballardini et al., 1994, Lehn, 1992). \sch
A view of the hydrogen-bonded structure of (I) and its numbering scheme are shown in Fig. 1. The complex owes its formation to hydrogen bonds between atoms O1 and O2 of the benzoate ion and atoms H13 and H14 of the 2-aminopyridinium ion, respectively. There is an eight-membered ring in the structure. This ring is formed as a result of the O1···H13 and O2···H14 hydrogen bonds. In addition to these hydrogen bonds, there is an intramolecular N—H···O hydrogen bond connecting units of (I). The hydrogen-bond distances in (I) are shorter than in 2-aminopyridinium salicylate [O1···N1 2.699 (4) and O2···N2 2.868 (16) Å; Gellert & Hsu, 1988].
2-Aminopyridine is protonated in acidic solutions. The bonding of the H atom to the ring N atom of 2-aminopyridine, but not to the amino N atom, gives an ion for which an additional resonance structure can be written (Acheson, 1967). The present investigation, like our previous work (Büyükgüngör & Odabaşoǧlu, 2002; Odabaşoǧlu et al., 2002), clearly shows that the positive charge in the 2-aminopyridinium ion is on the amino group.
The phenyl and pyridine rings of (I) display an almost coplanar configuration, with a dihedral angle of 8.4 (2)°. The C1—N2 bond is 1.3332 (15) Å, and this value is approximately equal to that of the C═N double bond (Shanmuga Sundara Raj, Fun, Lu et al., 2000), indicating that atom N2 of the amino group must also be sp2 hybridized. This is also supported by the C1—N2—H14 angle of 120.3 (9)° and by the fact that atoms C1, N2, H14 and H15 lie almost in the pyridine plane, with a maximum deviation of 0.09 (1) Å for atom H15. Similar bond distances and angles have been observed in 2-aminopyridinium succinate-succinic acid (Büyükgüngör & Odabaşoǧlu, 2002) and 2-aminopyridinium adipate monoadipic acid dihydrate (Odabaşoǧlu et al., 2002), and in some 2-aminopyridine-containing molecules (Yang et al., 1995; Grobelny et al., 1995; Shanmuga Sundara Raj, Fun, Zhao et al., 2000).