Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011000987X/fa3217sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011000987X/fa3217Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011000987X/fa3217IIsup3.hkl |
CCDC references: 774919; 774920
For related literature, see: Allen (2002); Bednowitz & Post (1966); Bernstein et al. (1995); Bowes et al. (2003); Chao et al. (1975); Gillespie (1992); Gorres et al. (1975); Hunter et al. (2001); Janczak & Perpétuo (2002, 2003, 2009a, 2009b); Janiak (2000); Kvick & Backéus (1974); Kvick et al. (1976); Marchewka et al. (2003); Perpétuo & Janczak (2006); van der Sluis & Kroon (1985, 1989).
Suitable crystals of (I) and (II) were obtained by slow evaporation of solutions of 5-chloropyridin-2-amine in 5% fumaric acid and of 2-aminopyridine in 5% DL-malic acid.
H atoms involved in hydrogen bonds in both structures were located in difference Fourier maps and refined with independent positional parameters but with distance restraints applied to O1—H1O in (I) and to N2—H1N and N2—H2N in (II). H atoms bonded to C in both structures were placed at calculated positions and refined as riders [riding] with C—H = 0.93 Å in (I) and for (II): C2—H2 0.98, C3—H 0.97, and pyridinium C—H 0.93 Å. Uiso(H) for all H atoms in both structures were constrained to xUeq of their respective carrier atoms, with x = 1.2 for all H in (I) and for (II): x = 1.2 for H bound to pyridinium ring atoms and x = 1.5 for all other H.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
2C5H5ClN2·C4H4O4 | F(000) = 384 |
Mr = 373.24 | Dx = 1.553 Mg m−3 Dm = 1.55 Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 652 reflections |
a = 13.806 (3) Å | θ = 3.0–29.6° |
b = 5.066 (1) Å | µ = 0.44 mm−1 |
c = 11.705 (2) Å | T = 295 K |
β = 102.87 (3)° | Paralellepied, colourless |
V = 798.1 (3) Å3 | 0.38 × 0.27 × 0.18 mm |
Z = 2 |
KUMA KM-4 with area CCD detector diffractometer | 2063 independent reflections |
Radiation source: fine-focus sealed tube | 1651 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.009 |
Detector resolution: 1-24x1-24 with blocks 2x2 pixels mm-1 | θmax = 29.6°, θmin = 3.0° |
ω–scan | h = −18→18 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2008) | k = −4→6 |
Tmin = 0.855, Tmax = 0.928 | l = −15→16 |
8665 measured reflections |
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0648P)2 + 0.250P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2063 reflections | Δρmax = 0.34 e Å−3 |
119 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (3) |
2C5H5ClN2·C4H4O4 | V = 798.1 (3) Å3 |
Mr = 373.24 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.806 (3) Å | µ = 0.44 mm−1 |
b = 5.066 (1) Å | T = 295 K |
c = 11.705 (2) Å | 0.38 × 0.27 × 0.18 mm |
β = 102.87 (3)° |
KUMA KM-4 with area CCD detector diffractometer | 2063 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2008) | 1651 reflections with I > 2σ(I) |
Tmin = 0.855, Tmax = 0.928 | Rint = 0.009 |
8665 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.34 e Å−3 |
2063 reflections | Δρmin = −0.36 e Å−3 |
119 parameters |
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 > 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 | 0.15302 (8) | 0.0878 (2) | 0.02724 (9) | 0.0415 (3) | |
H1O | 0.1799 (13) | −0.027 (3) | 0.0746 (14) | 0.050* | |
O2 | 0.05197 (9) | 0.1374 (3) | 0.15010 (10) | 0.0505 (3) | |
C7 | 0.08027 (11) | 0.2015 (3) | 0.06229 (12) | 0.0358 (3) | |
C8 | 0.03254 (10) | 0.4199 (3) | −0.01511 (13) | 0.0384 (3) | |
H8 | 0.0492 | 0.4441 | −0.0871 | 0.046* | |
N1 | 0.24636 (9) | −0.3011 (3) | 0.15176 (11) | 0.0376 (3) | |
C2 | 0.22565 (11) | −0.4011 (3) | 0.25012 (12) | 0.0388 (3) | |
C3 | 0.27956 (12) | −0.6192 (3) | 0.30670 (13) | 0.0446 (4) | |
H3 | 0.2660 | −0.6862 | 0.3755 | 0.054* | |
C4 | 0.35175 (12) | −0.7310 (3) | 0.25962 (15) | 0.0445 (4) | |
H4 | 0.3875 | −0.8756 | 0.2955 | 0.053* | |
C5 | 0.37116 (10) | −0.6252 (3) | 0.15695 (13) | 0.0395 (3) | |
C6 | 0.31839 (11) | −0.4139 (3) | 0.10568 (13) | 0.0393 (3) | |
H6 | 0.3319 | −0.3446 | 0.0373 | 0.047* | |
N2 | 0.15435 (12) | −0.2831 (3) | 0.29338 (14) | 0.0523 (4) | |
H21 | 0.1189 (16) | −0.139 (5) | 0.2525 (19) | 0.063* | |
H22 | 0.1400 (16) | −0.361 (5) | 0.349 (2) | 0.063* | |
Cl1 | 0.46095 (3) | −0.76762 (10) | 0.09378 (4) | 0.05647 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0454 (6) | 0.0424 (6) | 0.0388 (5) | 0.0122 (5) | 0.0140 (4) | 0.0078 (4) |
O2 | 0.0558 (7) | 0.0523 (7) | 0.0502 (7) | 0.0147 (5) | 0.0265 (5) | 0.0156 (5) |
C7 | 0.0373 (7) | 0.0344 (7) | 0.0360 (7) | −0.0017 (6) | 0.0086 (5) | 0.0020 (5) |
C8 | 0.0423 (7) | 0.0357 (7) | 0.0387 (7) | 0.0011 (6) | 0.0120 (6) | 0.0049 (6) |
N1 | 0.0423 (6) | 0.0386 (6) | 0.0335 (6) | 0.0039 (5) | 0.0122 (5) | 0.0024 (5) |
C2 | 0.0442 (7) | 0.0389 (8) | 0.0337 (7) | −0.0025 (6) | 0.0096 (6) | 0.0004 (6) |
C3 | 0.0534 (8) | 0.0452 (8) | 0.0353 (7) | 0.0011 (7) | 0.0100 (6) | 0.0088 (6) |
C4 | 0.0451 (8) | 0.0418 (8) | 0.0433 (8) | 0.0053 (6) | 0.0029 (6) | 0.0063 (6) |
C5 | 0.0370 (7) | 0.0415 (8) | 0.0391 (7) | −0.0001 (6) | 0.0062 (6) | −0.0030 (6) |
C6 | 0.0433 (7) | 0.0395 (8) | 0.0359 (7) | 0.0017 (6) | 0.0105 (6) | 0.0028 (6) |
N2 | 0.0641 (9) | 0.0516 (9) | 0.0496 (8) | 0.0110 (7) | 0.0307 (7) | 0.0092 (7) |
Cl1 | 0.0494 (3) | 0.0605 (3) | 0.0626 (3) | 0.01059 (18) | 0.0189 (2) | −0.0065 (2) |
O1—C7 | 1.3008 (18) | C3—C4 | 1.365 (2) |
O1—H1O | 0.83 (1) | C3—H3 | 0.9300 |
O2—C7 | 1.2220 (18) | C4—C5 | 1.395 (2) |
C7—C8 | 1.488 (2) | C4—H4 | 0.9300 |
C8—C8i | 1.316 (3) | C5—C6 | 1.357 (2) |
C8—H8 | 0.9300 | C5—Cl1 | 1.7355 (16) |
N1—C2 | 1.3455 (19) | C6—H6 | 0.9300 |
N1—C6 | 1.3584 (19) | N2—H21 | 0.95 (2) |
C2—N2 | 1.343 (2) | N2—H22 | 0.82 (2) |
C2—C3 | 1.412 (2) | ||
C7—O1—H1O | 111.1 (13) | C2—C3—H3 | 120.3 |
O2—C7—O1 | 124.19 (14) | C3—C4—C5 | 119.10 (15) |
O2—C7—C8 | 121.89 (14) | C3—C4—H4 | 120.4 |
O1—C7—C8 | 113.92 (12) | C5—C4—H4 | 120.4 |
C8i—C8—C7 | 122.08 (17) | C6—C5—C4 | 119.77 (14) |
C8i—C8—H8 | 119.0 | C6—C5—Cl1 | 120.23 (12) |
C7—C8—H8 | 119.0 | C4—C5—Cl1 | 119.99 (12) |
C2—N1—C6 | 119.69 (13) | C5—C6—N1 | 121.63 (14) |
N2—C2—N1 | 117.91 (14) | C5—C6—H6 | 119.2 |
N2—C2—C3 | 121.69 (14) | N1—C6—H6 | 119.2 |
N1—C2—C3 | 120.38 (14) | C2—N2—H21 | 119.5 (13) |
C4—C3—C2 | 119.42 (14) | C2—N2—H22 | 114.2 (16) |
C4—C3—H3 | 120.3 | H21—N2—H22 | 126 (2) |
O2—C7—C8—C8i | 10.0 (3) | C2—C3—C4—C5 | 0.5 (2) |
O1—C7—C8—C8i | −170.32 (18) | C3—C4—C5—C6 | 0.1 (2) |
C6—N1—C2—N2 | 179.60 (14) | C3—C4—C5—Cl1 | −178.76 (12) |
C6—N1—C2—C3 | 1.2 (2) | C4—C5—C6—N1 | −0.1 (2) |
N2—C2—C3—C4 | −179.54 (16) | Cl1—C5—C6—N1 | 178.75 (11) |
N1—C2—C3—C4 | −1.2 (2) | C2—N1—C6—C5 | −0.5 (2) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.83 (1) | 1.80 (1) | 2.6136 (16) | 168 (2) |
N2—H21···O2 | 0.95 (2) | 1.94 (2) | 2.880 (2) | 172.1 (19) |
N2—H22···O1ii | 0.82 (2) | 2.36 (2) | 3.146 (2) | 162 (2) |
Symmetry code: (ii) x, −y−1/2, z+1/2. |
C5H7N2+·C4H5O5− | F(000) = 480 |
Mr = 228.21 | Dx = 1.419 Mg m−3 Dm = 1.41 Mg m−3 Dm measured by flotation |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 782 reflections |
a = 7.6190 (15) Å | θ = 2.9–29.4° |
b = 7.4730 (15) Å | µ = 0.12 mm−1 |
c = 19.042 (4) Å | T = 295 K |
β = 99.85 (3)° | Paralellepiped, colourless |
V = 1068.2 (4) Å3 | 0.35 × 0.26 × 0.21 mm |
Z = 4 |
KUMA KM-4 with area CCD detector diffractometer | 2730 independent reflections |
Radiation source: fine-focus sealed tube | 1436 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 29.4°, θmin = 2.9° |
ω–scan | h = −9→10 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2008) | k = −9→9 |
Tmin = 0.962, Tmax = 0.974 | l = −25→25 |
13230 measured reflections |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.019P)2] where P = (Fo2 + 2Fc2)/3 |
2730 reflections | (Δ/σ)max < 0.001 |
160 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C5H7N2+·C4H5O5− | V = 1068.2 (4) Å3 |
Mr = 228.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.6190 (15) Å | µ = 0.12 mm−1 |
b = 7.4730 (15) Å | T = 295 K |
c = 19.042 (4) Å | 0.35 × 0.26 × 0.21 mm |
β = 99.85 (3)° |
KUMA KM-4 with area CCD detector diffractometer | 2730 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2008) | 1436 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.974 | Rint = 0.055 |
13230 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.19 e Å−3 |
2730 reflections | Δρmin = −0.21 e Å−3 |
160 parameters |
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 > 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 | 0.61017 (17) | 0.9701 (2) | 0.19686 (7) | 0.0453 (5) | |
O2 | 0.75745 (19) | 1.0347 (2) | 0.30518 (7) | 0.0452 (5) | |
C1 | 0.7518 (3) | 0.9826 (3) | 0.24309 (12) | 0.0347 (6) | |
C2 | 0.9294 (3) | 0.9411 (3) | 0.21877 (11) | 0.0330 (6) | |
H2 | 1.0112 | 0.8864 | 0.2583 | 0.049* | |
O5 | 0.9133 (2) | 0.8278 (2) | 0.15820 (8) | 0.0415 (5) | |
H5O | 0.877 (3) | 0.733 (3) | 0.1724 (13) | 0.062* | |
C3 | 1.0070 (3) | 1.1179 (3) | 0.19883 (11) | 0.0370 (6) | |
H3A | 0.9285 | 1.1676 | 0.1580 | 0.056* | |
H3B | 1.0095 | 1.2009 | 0.2382 | 0.056* | |
C4 | 1.1904 (3) | 1.1041 (3) | 0.18136 (13) | 0.0392 (6) | |
O3 | 1.30418 (18) | 1.0295 (3) | 0.23311 (8) | 0.0505 (5) | |
H3O | 1.410 (3) | 1.019 (3) | 0.2227 (12) | 0.076* | |
O4 | 1.2308 (2) | 1.1593 (3) | 0.12726 (8) | 0.0716 (6) | |
N1 | 0.4824 (3) | 0.7760 (3) | 0.07924 (10) | 0.0514 (7) | |
H1 | 0.554 (3) | 0.825 (3) | 0.1174 (10) | 0.062* | |
C5 | 0.5430 (4) | 0.7742 (4) | 0.01713 (11) | 0.0449 (7) | |
C6 | 0.4270 (4) | 0.7034 (3) | −0.04227 (13) | 0.0540 (8) | |
H6 | 0.4627 | 0.6990 | −0.0866 | 0.065* | |
C7 | 0.2649 (4) | 0.6424 (4) | −0.03479 (13) | 0.0591 (8) | |
H7 | 0.1894 | 0.5968 | −0.0743 | 0.071* | |
C8 | 0.2083 (4) | 0.6461 (4) | 0.03078 (14) | 0.0704 (9) | |
H8 | 0.0971 | 0.6016 | 0.0357 | 0.084* | |
C9 | 0.3190 (4) | 0.7163 (4) | 0.08746 (13) | 0.0664 (9) | |
H9 | 0.2831 | 0.7234 | 0.1317 | 0.080* | |
N2 | 0.7034 (3) | 0.8375 (4) | 0.01534 (10) | 0.0564 (6) | |
H1N | 0.778 (3) | 0.874 (3) | 0.0566 (7) | 0.085* | |
H2N | 0.751 (3) | 0.831 (4) | −0.0263 (6) | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0208 (7) | 0.0680 (13) | 0.0465 (9) | −0.0005 (10) | 0.0045 (7) | −0.0094 (10) |
O2 | 0.0382 (8) | 0.0615 (13) | 0.0376 (8) | 0.0072 (9) | 0.0116 (7) | −0.0045 (9) |
C1 | 0.0308 (11) | 0.0343 (16) | 0.0411 (12) | 0.0000 (13) | 0.0120 (11) | 0.0059 (14) |
C2 | 0.0206 (10) | 0.0413 (16) | 0.0367 (12) | 0.0047 (12) | 0.0042 (10) | −0.0036 (13) |
O5 | 0.0381 (9) | 0.0441 (11) | 0.0449 (9) | −0.0011 (10) | 0.0143 (8) | −0.0049 (10) |
C3 | 0.0295 (11) | 0.0374 (15) | 0.0443 (12) | −0.0014 (13) | 0.0068 (11) | −0.0006 (13) |
C4 | 0.0298 (12) | 0.0424 (17) | 0.0464 (13) | −0.0022 (13) | 0.0092 (12) | −0.0065 (14) |
O3 | 0.0238 (8) | 0.0711 (14) | 0.0581 (11) | 0.0032 (10) | 0.0109 (8) | 0.0080 (10) |
O4 | 0.0585 (11) | 0.1069 (17) | 0.0549 (10) | 0.0044 (12) | 0.0255 (10) | 0.0224 (13) |
N1 | 0.0478 (13) | 0.0658 (18) | 0.0370 (10) | −0.0112 (13) | −0.0024 (11) | −0.0060 (13) |
C5 | 0.0617 (17) | 0.0421 (19) | 0.0309 (11) | 0.0055 (16) | 0.0078 (13) | 0.0029 (13) |
C6 | 0.0757 (19) | 0.046 (2) | 0.0375 (12) | 0.0022 (18) | 0.0004 (15) | −0.0031 (14) |
C7 | 0.0711 (19) | 0.057 (2) | 0.0408 (14) | −0.0004 (19) | −0.0142 (15) | −0.0041 (16) |
C8 | 0.0646 (19) | 0.088 (3) | 0.0553 (16) | −0.024 (2) | 0.0015 (16) | −0.0079 (19) |
C9 | 0.0685 (19) | 0.088 (3) | 0.0444 (14) | −0.008 (2) | 0.0153 (15) | −0.0081 (18) |
N2 | 0.0554 (15) | 0.0739 (18) | 0.0407 (12) | −0.0078 (16) | 0.0106 (11) | 0.0001 (14) |
O1—C1 | 1.274 (2) | N1—C9 | 1.356 (3) |
O2—C1 | 1.239 (2) | N1—H1 | 0.91 (2) |
C1—C2 | 1.535 (3) | C5—N2 | 1.316 (3) |
C2—O5 | 1.419 (2) | C5—C6 | 1.414 (3) |
C2—C3 | 1.522 (3) | C6—C7 | 1.347 (3) |
C2—H2 | 0.9800 | C6—H6 | 0.9300 |
O5—H5O | 0.82 (2) | C7—C8 | 1.389 (3) |
C3—C4 | 1.495 (3) | C7—H7 | 0.9300 |
C3—H3A | 0.9700 | C8—C9 | 1.356 (3) |
C3—H3B | 0.9700 | C8—H8 | 0.9300 |
C4—O4 | 1.198 (2) | C9—H9 | 0.9300 |
C4—O3 | 1.319 (2) | N2—H1N | 0.93 (2) |
O3—H3O | 0.86 (2) | N2—H2N | 0.93 (2) |
N1—C5 | 1.341 (3) | ||
O2—C1—O1 | 124.7 (2) | C5—N1—H1 | 117.3 (13) |
O2—C1—C2 | 117.58 (19) | C9—N1—H1 | 118.6 (13) |
O1—C1—C2 | 117.57 (19) | N2—C5—N1 | 118.7 (2) |
O5—C2—C3 | 107.38 (17) | N2—C5—C6 | 124.7 (2) |
O5—C2—C1 | 114.04 (17) | N1—C5—C6 | 116.5 (3) |
C3—C2—C1 | 107.43 (18) | C7—C6—C5 | 120.1 (3) |
O5—C2—H2 | 109.3 | C7—C6—H6 | 120.0 |
C3—C2—H2 | 109.3 | C5—C6—H6 | 120.0 |
C1—C2—H2 | 109.3 | C6—C7—C8 | 121.3 (3) |
C2—O5—H5O | 103.6 (17) | C6—C7—H7 | 119.4 |
C4—C3—C2 | 114.4 (2) | C8—C7—H7 | 119.4 |
C4—C3—H3A | 108.7 | C9—C8—C7 | 118.5 (3) |
C2—C3—H3A | 108.7 | C9—C8—H8 | 120.8 |
C4—C3—H3B | 108.7 | C7—C8—H8 | 120.8 |
C2—C3—H3B | 108.7 | C8—C9—N1 | 119.6 (2) |
H3A—C3—H3B | 107.6 | C8—C9—H9 | 120.2 |
O4—C4—O3 | 123.7 (2) | N1—C9—H9 | 120.2 |
O4—C4—C3 | 123.7 (2) | C5—N2—H1N | 121.3 (15) |
O3—C4—C3 | 112.5 (2) | C5—N2—H2N | 120.3 (15) |
C4—O3—H3O | 112.6 (16) | H1N—N2—H2N | 118 (2) |
C5—N1—C9 | 124.0 (2) | ||
O2—C1—C2—O5 | 159.66 (19) | C9—N1—C5—N2 | 179.3 (3) |
O1—C1—C2—O5 | −24.0 (3) | C9—N1—C5—C6 | −0.6 (4) |
O2—C1—C2—C3 | −81.5 (2) | N2—C5—C6—C7 | −179.8 (3) |
O1—C1—C2—C3 | 94.8 (2) | N1—C5—C6—C7 | 0.1 (4) |
O5—C2—C3—C4 | −63.3 (2) | C5—C6—C7—C8 | −0.4 (4) |
C1—C2—C3—C4 | 173.68 (18) | C6—C7—C8—C9 | 1.2 (5) |
C2—C3—C4—O4 | 126.6 (3) | C7—C8—C9—N1 | −1.7 (4) |
C2—C3—C4—O3 | −55.4 (3) | C5—N1—C9—C8 | 1.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5O···O2i | 0.82 (2) | 1.89 (2) | 2.699 (2) | 167 (2) |
O3—H3O···O1ii | 0.86 (2) | 1.72 (2) | 2.581 (2) | 172 (3) |
N1—H1···O1 | 0.91 (2) | 1.85 (2) | 2.706 (2) | 156 (2) |
N2—H1N···O5 | 0.93 (2) | 2.06 (1) | 2.911 (2) | 152 (2) |
N2—H2N···O4iii | 0.93 (2) | 1.95 (1) | 2.845 (3) | 161 (2) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+2, −y+2, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | 2C5H5ClN2·C4H4O4 | C5H7N2+·C4H5O5− |
Mr | 373.24 | 228.21 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 13.806 (3), 5.066 (1), 11.705 (2) | 7.6190 (15), 7.4730 (15), 19.042 (4) |
β (°) | 102.87 (3) | 99.85 (3) |
V (Å3) | 798.1 (3) | 1068.2 (4) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.44 | 0.12 |
Crystal size (mm) | 0.38 × 0.27 × 0.18 | 0.35 × 0.26 × 0.21 |
Data collection | ||
Diffractometer | KUMA KM-4 with area CCD detector diffractometer | KUMA KM-4 with area CCD detector diffractometer |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2008) | Numerical (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.855, 0.928 | 0.962, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8665, 2063, 1651 | 13230, 2730, 1436 |
Rint | 0.009 | 0.055 |
(sin θ/λ)max (Å−1) | 0.695 | 0.690 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.117, 1.00 | 0.059, 0.084, 1.00 |
No. of reflections | 2063 | 2730 |
No. of parameters | 119 | 160 |
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) | 0.34, −0.36 | 0.19, −0.21 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.83 (1) | 1.795 (10) | 2.6136 (16) | 168.3 (19) |
N2—H21···O2 | 0.95 (2) | 1.94 (2) | 2.880 (2) | 172.1 (19) |
N2—H22···O1i | 0.82 (2) | 2.36 (2) | 3.146 (2) | 162 (2) |
Symmetry code: (i) x, −y−1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5O···O2i | 0.82 (2) | 1.89 (2) | 2.699 (2) | 167 (2) |
O3—H3O···O1ii | 0.86 (2) | 1.72 (2) | 2.581 (2) | 172 (3) |
N1—H1···O1 | 0.91 (2) | 1.85 (2) | 2.706 (2) | 156 (2) |
N2—H1N···O5 | 0.93 (2) | 2.061 (13) | 2.911 (2) | 152 (2) |
N2—H2N···O4iii | 0.93 (2) | 1.951 (8) | 2.845 (3) | 161 (2) |
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+2, −y+2, −z. |
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As a continuation of our studies of hybrid crystals with acid–base ionic and hydrogen-bonding interactions whose utility has been described previously (Janczak & Perpétuo, 2002, 2003, 2009a, 2009b; Marchewka et al., 2003; Perpétuo & Janczak, 2006), in the present work we investigate the crystal structures of the bis(5-chloropyridin-2-amine) fumaric acid adduct, (I), and 2-aminopyridinium DL-malate, (II).
The asymmetric unit of (I) consists of the neutral 5-chloropyridin-2-amine molecule and half centrosymmetric molecule of fumaric acid (Fig. 1a). Proton transfer does not take place from the fumaric acid to the ring N atom of 5-chloropyridin-2-amine, and the internal C2—N1—C6 angle [119.69 (13)°] is comparable with that in the neutral 5-chloropyridin-2-amine molecule [118.3 (1)°, Kvick & Backéus, 1974; Kvick et al. 1976] and is in agreement with the valence shell electron pair repulsion model, VSEPR (Gillespie, 1992). The slightly increased C2—N1—C6 angle results from the relatively strong hydrogen bond diminishing the steric effect of the lone pair of electrons. The C—O bonds in the molecule of fumaric acid [C7—O1, 1.3008 (18) and C7—O2, 1.2220 (18) Å] are comparable to those found for pure fumaric acid (Bednowitz & Post, 1966) and in the adduct of picoline-N-oxide fumaric acid (Gorres et al. 1975), and to those observed in adducts with polyamines (Bowes et al., 2003). The fumaric acid interacts with two neighbouring 5-chloropyridin-2-amine molecules via almost linear N—H···O and O—H···N hydrogen bonds (Table 1) with a binary graph set of R22(8) (Bernstein et al. 1995) forming planar aggregates (C5H5ClN2).(C4H4O4).(C5H5ClN2). Two such planar aggregates related by a c-glide plane are inclined by 76.08 (7)° with each other [the dihedral angle between the pyridine ring at (x, y, z) and that at (x, 1/2 - y, 1/2 + z)]. These structural units, translated along the c axis, are linked via another N—H···O hydrogen bond between the amine group and the O1 atom of fumaric acid, developing two-dimensional layers extending parallel to the (100) plane. The planar aggregates are stacked along the b axis (Fig. 1b).
The asymmetric unit of (II) consists of a protonated 2-aminopyridinium cation and a single deprotonated malate anion, linked by N—H···O hydrogen bonds with a binary graph set of R22(9) (Fig. 2a). The proton transfer from the carboxyl group to the ring N atom of 2-aminopyridine is manifested in the delocalization of the charge over both C—O bonds of the COO- group as well as in an increased internal C5—N1—C9 angle [124.0 (2)°] compared to that in neutral 2-aminopyridine [117.5 (3)°, Chao et al. 1975]. The opening of the internal C—N—C angle results from a decrease of the steric effect of the lone pair of electrons and is consistent with the valence shell electron pair repulsion model (Gillespie, 1992). The conformation of the carbon skeleton of the malate anion in (II) is syn [Ψ = 173.68 (18)°] with the carboxylate group (COO-) almost coplanar with the C2 and O5 atoms [ϕ2 = -24.0 (3)°]. The conformation of the carboxyl group (COOH) around the terminal C—C bond is clinal [χ = -55.4 (3)°]. The Ψ, ϕ2 and χ torsion angles in (II) (Ψ = C1—C2—C3—C4, ϕ2 = O1—C1—C2—O5 and χ = C2—C3—C4—O3) describe the conformation of the malate(-) anion as well as the conformation of malic acid (van der Sluis & Kroon, 1985, 1989). In optimized malate(-) the values of Ψ, ϕ2 and χ are -177.8, -3.9 and 61.7°, respectively, and thus the conformation of the carbon skeleton of optimized malate(-) is anti (Janczak & Perpétuo, 2003). The optimized value of ϕ2 is smaller than in (II) due to the presence in the optimized structure of an intramolecular O5—H5o···O1 hydrogen bond (O5—H5o = 0.947 Å, H5o···O1 = 1.872Å and O5—H5o···O1 = 125.6°). Malate anions related by a translation along the a axis interact via O3—H3o···O1ii and symmetry-equivalent hydrogen bonds with a graph set of C(7) between the carboxyl group (COOH) and the carboxylate group (COO-) of the neighbour, forming chains along the a axis. These chains are interconnected by O5—H5O···O2i and symmetry-eqivalent hydrogen bonds (Table 2) between the hydroxyl groups and one O atom of the carboxylate group (COO-), forming two-dimensional sheets extending parallel to (001) at z = 1/4 and 3/4 (Fig. 2b). The malate(-) anions in the sheet are interconnected via a pair of O—H···O hydrogen bonds with a graph set of C(5) and C(7) yielding an R44(22) hydrogen-bonded tetramer propagated by translation, forming a two-dimensional layer (Fig. 2c). The 2-aminopyridinium cations are perpendicular to the anionic sheets and interact via N—H···O hydrogen bonds forming a three-dimensional network (Fig. 2b). The 2-aminopyridinium cation at (xyz) is related by inversion to that at (1 - x, 1 - y, -z) and to another at (1 - x, 2 - y, -z), with interplanar distances 3.401, 3.400 Å and slip distances of 1.801 and 3.504 Å, respectively. The former involves a stabilizing π–π interaction between the rings (Janiak, 2000; Hunter et al. 2001). In the second interaction, the rings do not overlap, but the 2-amino group of each cation is parallel to and eclipsed with the ring of the other.
This work illustrates the utility of 2-aminopyridine and its 5-chloro derivative for the formation of two- or three-dimensional hydrogen-bonded networks formed with co-crystallization partners, i.e. fumaric or DL-malic acids. A search of the CCDC (Version 5.31, November 2009) for structures containing 2-aminopyridine co-crystallized with anionic partners gives over 70 structures with a large number of inorganic and organic anions, but for 5-chloropyridin-2-amine yields only ten structures (Allen, 2002). Generally, the dimensionality of the networks in these crystals is determined by the conformation of the co-crystallization partners.