Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704785X/hb2562sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704785X/hb2562Isup2.hkl |
CCDC reference: 667294
A 5 ml e thanol solution of 3-aminopyridine (1.0 mmol, 0.094 g) was added to 20 ml hot aqueous solution of benzylic acid (1.0 mmol, 0.23 g) and the mixture was stirred for 15 minutes at 373 K. Then the solution was filtered, and the filtrate was kept at the room temperature. After a week, colourless plates of (I) were obtained.
Friedel-pair reflections were merged, since anormalous scattering effects were negligible. H atoms bonded to nitrogen atoms, hydroxyl group and water oxygen were located in a difference synthesis and refined isotropically with N—H = 0.85 (1) Å, O—H = 0.82 Å and H···H = 1.34 (1) Å, respectively. All the remaining H atoms were placed in calculated positions with C—H = 0.93 Å and were refined as riding with Uiso = 1.2Ueq(C).
Supramolecular hydrogen bonded networks are an important area of current research (Zeng et al., 2005). Herein we report the supramolecular structure of the title compound, (I).
The asymmetric unit of (I) consists of one 2-aminopyridinium cation, one benzylate anion and one crystallization water (Fig. 1), in which 3-aminopyridinium cation interacts with benzylate anion through the doubly intermolecular Nprotonized—H···Ohydroxyl (N1—H1A···O3) and Nprotonized—H···Ocarboxylate (N1—H1A···O2) hydrogen bonds, and builds a R12(5) ring (Table 1). The crystallization water, in which one of H atoms (H4A) acts as hydrogen bond donor is hydrogen bonded to carboxylate oxygen (O2) of benzylate anion. The other H atom (H4B) of water and hydroxyl H atom (H3A) of benzylate anion linked the adjacent asymmetric units by Owater—H···Ocarboxylate and OhydroxylH···Owater hydrogen bonds, respectively, into an infinite one-dimensional chain along the direction [001] (Fig. 2). Finally, infinite one-dimensional chains are further extended into a two-dimensional network running parallel to the plane (100) by Namino—H···Ocarboxylate hydrogen bonds (Fig.3).
For background, see: Zeng et al. (2005).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).
C5H7N2+·C14H11O3−·H2O | F(000) = 720 |
Mr = 340.37 | Dx = 1.327 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 2804 reflections |
a = 28.903 (6) Å | θ = 2.6–22.3° |
b = 8.6828 (18) Å | µ = 0.09 mm−1 |
c = 6.7900 (14) Å | T = 298 K |
V = 1704.0 (6) Å3 | Plate, colourless |
Z = 4 | 0.48 × 0.32 × 0.03 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1821 independent reflections |
Radiation source: fine-focus sealed tube | 1607 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω' scans | θmax = 26.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −35→16 |
Tmin = 0.956, Tmax = 0.997 | k = −7→10 |
6660 measured reflections | l = −8→8 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0484P)2 + 0.0365P] where P = (Fo2 + 2Fc2)/3 |
1821 reflections | (Δ/σ)max < 0.001 |
250 parameters | Δρmax = 0.13 e Å−3 |
7 restraints | Δρmin = −0.17 e Å−3 |
C5H7N2+·C14H11O3−·H2O | V = 1704.0 (6) Å3 |
Mr = 340.37 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 28.903 (6) Å | µ = 0.09 mm−1 |
b = 8.6828 (18) Å | T = 298 K |
c = 6.7900 (14) Å | 0.48 × 0.32 × 0.03 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1821 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1607 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.997 | Rint = 0.028 |
6660 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 7 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.13 e Å−3 |
1821 reflections | Δρmin = −0.17 e Å−3 |
250 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 | 0.17063 (6) | 0.2495 (2) | 0.7187 (3) | 0.0457 (5) | |
O2 | 0.20716 (5) | 0.4364 (2) | 0.8757 (3) | 0.0475 (5) | |
O3 | 0.13841 (5) | 0.48577 (18) | 1.1257 (3) | 0.0378 (4) | |
H3A | 0.1587 (7) | 0.438 (3) | 1.186 (4) | 0.056 (9)* | |
O4 | 0.29689 (6) | 0.3420 (3) | 0.8495 (3) | 0.0616 (6) | |
H4A | 0.2694 (4) | 0.363 (3) | 0.848 (5) | 0.059 (9)* | |
H4B | 0.3028 (11) | 0.307 (4) | 0.959 (3) | 0.062 (10)* | |
C6 | 0.17223 (7) | 0.3540 (3) | 0.8424 (4) | 0.0334 (5) | |
C7 | 0.12734 (7) | 0.3950 (2) | 0.9587 (4) | 0.0310 (5) | |
C14 | 0.10135 (7) | 0.2479 (3) | 1.0166 (4) | 0.0344 (6) | |
C19 | 0.09745 (8) | 0.2027 (3) | 1.2115 (4) | 0.0432 (6) | |
H19 | 0.1100 | 0.2637 | 1.3106 | 0.052* | |
C18 | 0.07485 (9) | 0.0665 (3) | 1.2595 (5) | 0.0551 (8) | |
H18 | 0.0726 | 0.0369 | 1.3908 | 0.066* | |
C17 | 0.05596 (10) | −0.0240 (3) | 1.1177 (6) | 0.0618 (9) | |
H17 | 0.0413 | −0.1157 | 1.1511 | 0.074* | |
C16 | 0.05879 (10) | 0.0216 (3) | 0.9236 (6) | 0.0588 (8) | |
H16 | 0.0457 | −0.0392 | 0.8256 | 0.071* | |
C15 | 0.08091 (8) | 0.1569 (3) | 0.8737 (5) | 0.0452 (6) | |
H15 | 0.0821 | 0.1873 | 0.7425 | 0.054* | |
C8 | 0.09618 (7) | 0.4964 (3) | 0.8301 (4) | 0.0325 (5) | |
C13 | 0.05536 (8) | 0.5509 (3) | 0.9120 (5) | 0.0445 (7) | |
H13 | 0.0482 | 0.5276 | 1.0422 | 0.053* | |
C12 | 0.02522 (9) | 0.6397 (3) | 0.8016 (6) | 0.0551 (8) | |
H12 | −0.0022 | 0.6743 | 0.8576 | 0.066* | |
C11 | 0.03548 (10) | 0.6771 (3) | 0.6100 (6) | 0.0594 (9) | |
H11 | 0.0151 | 0.7370 | 0.5365 | 0.071* | |
C10 | 0.07602 (10) | 0.6254 (3) | 0.5276 (5) | 0.0542 (8) | |
H10 | 0.0833 | 0.6511 | 0.3983 | 0.065* | |
C9 | 0.10598 (9) | 0.5353 (3) | 0.6367 (4) | 0.0440 (6) | |
H9 | 0.1332 | 0.5002 | 0.5792 | 0.053* | |
N1 | 0.22005 (8) | 0.7051 (3) | 1.0551 (3) | 0.0437 (5) | |
H1A | 0.2120 (9) | 0.6156 (18) | 1.015 (4) | 0.051 (8)* | |
N2 | 0.32649 (8) | 0.9158 (3) | 1.1201 (4) | 0.0565 (6) | |
H2A | 0.3349 (11) | 1.005 (2) | 1.157 (6) | 0.072 (10)* | |
H2B | 0.3463 (8) | 0.843 (2) | 1.104 (5) | 0.058 (10)* | |
C1 | 0.26516 (8) | 0.7347 (3) | 1.0651 (4) | 0.0409 (6) | |
H1 | 0.2864 | 0.6564 | 1.0415 | 0.049* | |
C2 | 0.28080 (8) | 0.8822 (3) | 1.1107 (4) | 0.0398 (6) | |
C3 | 0.24702 (10) | 0.9941 (3) | 1.1417 (5) | 0.0456 (6) | |
H3 | 0.2559 | 1.0947 | 1.1696 | 0.055* | |
C4 | 0.20121 (9) | 0.9583 (3) | 1.1315 (5) | 0.0497 (7) | |
H4 | 0.1791 | 1.0339 | 1.1547 | 0.060* | |
C5 | 0.18779 (10) | 0.8111 (3) | 1.0872 (4) | 0.0490 (7) | |
H5 | 0.1566 | 0.7857 | 1.0797 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0465 (10) | 0.0357 (9) | 0.0550 (11) | 0.0014 (8) | 0.0115 (9) | −0.0106 (9) |
O2 | 0.0306 (8) | 0.0482 (11) | 0.0635 (13) | −0.0051 (7) | 0.0052 (8) | −0.0112 (10) |
O3 | 0.0363 (9) | 0.0364 (9) | 0.0406 (10) | −0.0005 (7) | −0.0030 (8) | −0.0090 (8) |
O4 | 0.0340 (10) | 0.0979 (18) | 0.0530 (15) | 0.0072 (10) | 0.0054 (10) | 0.0192 (13) |
C6 | 0.0330 (11) | 0.0254 (11) | 0.0418 (15) | 0.0032 (10) | 0.0010 (11) | 0.0034 (11) |
C7 | 0.0303 (11) | 0.0272 (12) | 0.0354 (13) | −0.0011 (9) | 0.0003 (10) | −0.0039 (10) |
C14 | 0.0257 (10) | 0.0318 (12) | 0.0458 (15) | 0.0023 (9) | 0.0045 (10) | −0.0006 (12) |
C19 | 0.0386 (13) | 0.0416 (14) | 0.0493 (16) | −0.0028 (11) | 0.0037 (12) | 0.0042 (14) |
C18 | 0.0568 (16) | 0.0475 (17) | 0.061 (2) | −0.0075 (14) | 0.0100 (15) | 0.0128 (15) |
C17 | 0.0579 (17) | 0.0372 (15) | 0.090 (3) | −0.0154 (13) | 0.0123 (19) | 0.0087 (17) |
C16 | 0.0597 (18) | 0.0397 (15) | 0.077 (2) | −0.0144 (14) | 0.0030 (16) | −0.0113 (16) |
C15 | 0.0469 (13) | 0.0384 (14) | 0.0502 (17) | −0.0052 (11) | 0.0011 (13) | −0.0033 (13) |
C8 | 0.0296 (11) | 0.0231 (11) | 0.0448 (14) | −0.0029 (9) | −0.0041 (11) | −0.0049 (11) |
C13 | 0.0356 (13) | 0.0389 (13) | 0.0590 (18) | 0.0016 (11) | 0.0024 (12) | −0.0019 (14) |
C12 | 0.0342 (13) | 0.0440 (16) | 0.087 (3) | 0.0088 (12) | −0.0051 (14) | −0.0078 (17) |
C11 | 0.0566 (17) | 0.0378 (15) | 0.084 (3) | 0.0088 (13) | −0.0290 (18) | −0.0016 (17) |
C10 | 0.0696 (19) | 0.0459 (16) | 0.0470 (18) | 0.0066 (15) | −0.0138 (15) | 0.0057 (14) |
C9 | 0.0464 (14) | 0.0409 (15) | 0.0448 (16) | 0.0057 (12) | −0.0001 (13) | −0.0017 (13) |
N1 | 0.0516 (13) | 0.0386 (13) | 0.0409 (13) | −0.0107 (11) | −0.0026 (10) | −0.0010 (11) |
N2 | 0.0500 (14) | 0.0500 (16) | 0.0696 (17) | −0.0082 (13) | 0.0021 (13) | −0.0076 (15) |
C1 | 0.0495 (15) | 0.0355 (13) | 0.0378 (14) | 0.0014 (11) | 0.0012 (11) | 0.0014 (12) |
C2 | 0.0461 (13) | 0.0421 (14) | 0.0314 (13) | −0.0053 (12) | 0.0012 (12) | −0.0002 (12) |
C3 | 0.0622 (15) | 0.0324 (12) | 0.0422 (15) | −0.0013 (13) | 0.0058 (14) | −0.0028 (13) |
C4 | 0.0539 (15) | 0.0450 (16) | 0.0502 (16) | 0.0059 (13) | 0.0034 (14) | 0.0017 (14) |
C5 | 0.0473 (14) | 0.0541 (16) | 0.0456 (17) | −0.0038 (14) | 0.0023 (13) | 0.0029 (14) |
O1—C6 | 1.237 (3) | C13—H13 | 0.9300 |
O2—C6 | 1.258 (3) | C12—C11 | 1.374 (5) |
O3—C7 | 1.417 (3) | C12—H12 | 0.9300 |
O3—H3A | 0.826 (10) | C11—C10 | 1.374 (4) |
O4—H4A | 0.816 (10) | C11—H11 | 0.9300 |
O4—H4B | 0.820 (10) | C10—C9 | 1.382 (4) |
C6—C7 | 1.560 (3) | C10—H10 | 0.9300 |
C7—C8 | 1.533 (3) | C9—H9 | 0.9300 |
C7—C14 | 1.533 (3) | N1—C5 | 1.328 (4) |
C14—C15 | 1.384 (4) | N1—C1 | 1.331 (3) |
C14—C19 | 1.384 (4) | N1—H1A | 0.855 (10) |
C19—C18 | 1.390 (4) | N2—C2 | 1.354 (3) |
C19—H19 | 0.9300 | N2—H2A | 0.848 (10) |
C18—C17 | 1.357 (5) | N2—H2B | 0.858 (10) |
C18—H18 | 0.9300 | C1—C2 | 1.393 (4) |
C17—C16 | 1.379 (5) | C1—H1 | 0.9300 |
C17—H17 | 0.9300 | C2—C3 | 1.393 (4) |
C16—C15 | 1.379 (4) | C3—C4 | 1.361 (4) |
C16—H16 | 0.9300 | C3—H3 | 0.9300 |
C15—H15 | 0.9300 | C4—C5 | 1.370 (4) |
C8—C9 | 1.385 (4) | C4—H4 | 0.9300 |
C8—C13 | 1.388 (3) | C5—H5 | 0.9300 |
C13—C12 | 1.384 (4) | ||
C7—O3—H3A | 106 (2) | C8—C13—H13 | 119.7 |
H4A—O4—H4B | 107 (3) | C11—C12—C13 | 120.6 (3) |
O1—C6—O2 | 124.7 (2) | C11—C12—H12 | 119.7 |
O1—C6—C7 | 118.69 (19) | C13—C12—H12 | 119.7 |
O2—C6—C7 | 116.5 (2) | C12—C11—C10 | 119.5 (3) |
O3—C7—C8 | 105.64 (17) | C12—C11—H11 | 120.3 |
O3—C7—C14 | 111.62 (19) | C10—C11—H11 | 120.3 |
C8—C7—C14 | 109.68 (18) | C11—C10—C9 | 120.1 (3) |
O3—C7—C6 | 110.14 (17) | C11—C10—H10 | 120.0 |
C8—C7—C6 | 109.4 (2) | C9—C10—H10 | 120.0 |
C14—C7—C6 | 110.29 (17) | C10—C9—C8 | 121.2 (3) |
C15—C14—C19 | 118.2 (2) | C10—C9—H9 | 119.4 |
C15—C14—C7 | 120.3 (2) | C8—C9—H9 | 119.4 |
C19—C14—C7 | 121.4 (2) | C5—N1—C1 | 123.1 (2) |
C14—C19—C18 | 120.2 (3) | C5—N1—H1A | 119.4 (19) |
C14—C19—H19 | 119.9 | C1—N1—H1A | 117.3 (19) |
C18—C19—H19 | 119.9 | C2—N2—H2A | 119 (2) |
C17—C18—C19 | 121.0 (3) | C2—N2—H2B | 119 (2) |
C17—C18—H18 | 119.5 | H2A—N2—H2B | 121 (3) |
C19—C18—H18 | 119.5 | N1—C1—C2 | 120.5 (2) |
C18—C17—C16 | 119.2 (3) | N1—C1—H1 | 119.8 |
C18—C17—H17 | 120.4 | C2—C1—H1 | 119.8 |
C16—C17—H17 | 120.4 | N2—C2—C3 | 121.8 (2) |
C17—C16—C15 | 120.5 (3) | N2—C2—C1 | 121.7 (2) |
C17—C16—H16 | 119.8 | C3—C2—C1 | 116.5 (2) |
C15—C16—H16 | 119.8 | C4—C3—C2 | 121.0 (2) |
C16—C15—C14 | 120.8 (3) | C4—C3—H3 | 119.5 |
C16—C15—H15 | 119.6 | C2—C3—H3 | 119.5 |
C14—C15—H15 | 119.6 | C3—C4—C5 | 119.9 (3) |
C9—C8—C13 | 118.1 (2) | C3—C4—H4 | 120.0 |
C9—C8—C7 | 124.1 (2) | C5—C4—H4 | 120.0 |
C13—C8—C7 | 117.8 (2) | N1—C5—C4 | 119.0 (3) |
C12—C13—C8 | 120.5 (3) | N1—C5—H5 | 120.5 |
C12—C13—H13 | 119.7 | C4—C5—H5 | 120.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O4i | 0.83 (1) | 1.89 (1) | 2.714 (3) | 173 (3) |
O4—H4A···O2 | 0.82 (1) | 1.92 (1) | 2.726 (2) | 171 (3) |
O4—H4B···O1i | 0.82 (1) | 1.99 (1) | 2.795 (3) | 168 (3) |
N1—H1A···O2 | 0.86 (1) | 1.83 (1) | 2.658 (3) | 163 (3) |
N1—H1A···O3 | 0.86 (1) | 2.52 (2) | 3.070 (3) | 123 (2) |
N2—H2A···O1ii | 0.85 (1) | 2.17 (2) | 2.975 (3) | 158 (3) |
Symmetry codes: (i) −x+1/2, y, z+1/2; (ii) −x+1/2, y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C5H7N2+·C14H11O3−·H2O |
Mr | 340.37 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 298 |
a, b, c (Å) | 28.903 (6), 8.6828 (18), 6.7900 (14) |
V (Å3) | 1704.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.48 × 0.32 × 0.03 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.956, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6660, 1821, 1607 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.086, 1.08 |
No. of reflections | 1821 |
No. of parameters | 250 |
No. of restraints | 7 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.13, −0.17 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O4i | 0.826 (10) | 1.891 (12) | 2.714 (3) | 173 (3) |
O4—H4A···O2 | 0.816 (10) | 1.918 (12) | 2.726 (2) | 171 (3) |
O4—H4B···O1i | 0.820 (10) | 1.989 (13) | 2.795 (3) | 168 (3) |
N1—H1A···O2 | 0.855 (10) | 1.827 (13) | 2.658 (3) | 163 (3) |
N1—H1A···O3 | 0.855 (10) | 2.52 (2) | 3.070 (3) | 123 (2) |
N2—H2A···O1ii | 0.848 (10) | 2.172 (16) | 2.975 (3) | 158 (3) |
Symmetry codes: (i) −x+1/2, y, z+1/2; (ii) −x+1/2, y+1, z+1/2. |
Supramolecular hydrogen bonded networks are an important area of current research (Zeng et al., 2005). Herein we report the supramolecular structure of the title compound, (I).
The asymmetric unit of (I) consists of one 2-aminopyridinium cation, one benzylate anion and one crystallization water (Fig. 1), in which 3-aminopyridinium cation interacts with benzylate anion through the doubly intermolecular Nprotonized—H···Ohydroxyl (N1—H1A···O3) and Nprotonized—H···Ocarboxylate (N1—H1A···O2) hydrogen bonds, and builds a R12(5) ring (Table 1). The crystallization water, in which one of H atoms (H4A) acts as hydrogen bond donor is hydrogen bonded to carboxylate oxygen (O2) of benzylate anion. The other H atom (H4B) of water and hydroxyl H atom (H3A) of benzylate anion linked the adjacent asymmetric units by Owater—H···Ocarboxylate and OhydroxylH···Owater hydrogen bonds, respectively, into an infinite one-dimensional chain along the direction [001] (Fig. 2). Finally, infinite one-dimensional chains are further extended into a two-dimensional network running parallel to the plane (100) by Namino—H···Ocarboxylate hydrogen bonds (Fig.3).