Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680201471X/ya6121sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680201471X/ya6121Isup2.hkl |
CCDC reference: 197474
The organic salt was the crystalline compound that resulted from the reaction of europium perchlorate (0.45 g, 1 mmol), 2-aminopyrimidine (0.20 g, 2 mmol) and trichloroacetic acid (0.33 g, 2 mmol). 2-Aminopyrimidine dissolved in a small volume of ethanol was added to europium perchlorate dissolved in water to afford a precipitate. Trichloroacetic acid dissolved in water was then added to dissolve the precipitate; the clear solution was filtered and then set aside. Colorless crystals of the title compound separated from the solution after several days.
The nitrogen-bound H-atoms were located and refined, subject to N—H = 0.85±0.01 Å; the aromatic H-atoms were generated geometrically and were allowed to ride on their parent C-atoms, with U(H) = 1.2Ueq(C). A residual peak of 1 e Å−3 was found at 1.1 Å from the Cl3 atom.
For the geometry-optimization calculations, the initial structure was taken from the X-ray results. It was optimized in its lowest energy state (singlet spin state) using the semi-empirical quantum chemical PM3 Hamiltonian in HYPERCHEM (Hypercube, Inc., 2001). The unrestricted Hartree–Fock method was employed in the optimization.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C4H6N3+·C2Cl3O2− | F(000) = 520 |
Mr = 258.49 | Dx = 1.677 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.468 (2) Å | Cell parameters from 1504 reflections |
b = 11.297 (2) Å | θ = 2.5–24.8° |
c = 10.957 (2) Å | µ = 0.87 mm−1 |
β = 102.314 (3)° | T = 298 K |
V = 1024.1 (3) Å3 | Block, colorless |
Z = 4 | 0.40 × 0.30 × 0.10 mm |
Siemens CCD area-detector diffractometer | 1081 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 24.8°, θmin = 2.5° |
ω scan | h = −9→9 |
5155 measured reflections | k = −13→12 |
1748 independent reflections | l = −10→12 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.181 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0924P)2 + 0.867P] where P = (Fo2 + 2Fc2)/3 |
1748 reflections | (Δ/σ)max < 0.001 |
139 parameters | Δρmax = 1.04 e Å−3 |
3 restraints | Δρmin = −0.51 e Å−3 |
C4H6N3+·C2Cl3O2− | V = 1024.1 (3) Å3 |
Mr = 258.49 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.468 (2) Å | µ = 0.87 mm−1 |
b = 11.297 (2) Å | T = 298 K |
c = 10.957 (2) Å | 0.40 × 0.30 × 0.10 mm |
β = 102.314 (3)° |
Siemens CCD area-detector diffractometer | 1081 reflections with I > 2σ(I) |
5155 measured reflections | Rint = 0.041 |
1748 independent reflections |
R[F2 > 2σ(F2)] = 0.058 | 3 restraints |
wR(F2) = 0.181 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 1.04 e Å−3 |
1748 reflections | Δρmin = −0.51 e Å−3 |
139 parameters |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.9403 (2) | 0.2646 (2) | 0.2322 (2) | 0.0722 (6) | |
Cl2 | 0.9414 (2) | 0.5017 (1) | 0.1497 (2) | 0.0728 (6) | |
Cl3 | 0.7626 (2) | 0.3246 (2) | −0.0119 (1) | 0.0752 (6) | |
O1 | 0.5992 (4) | 0.3078 (3) | 0.2269 (4) | 0.052 (1) | |
O2 | 0.6186 (6) | 0.5019 (3) | 0.1939 (5) | 0.078 (1) | |
N1 | 0.3828 (5) | 0.3477 (4) | 0.3752 (4) | 0.042 (1) | |
N2 | 0.2262 (6) | 0.4819 (4) | 0.4640 (4) | 0.054 (1) | |
N3 | 0.3827 (6) | 0.5467 (4) | 0.3302 (5) | 0.057 (1) | |
C1 | 0.6624 (6) | 0.3985 (5) | 0.1927 (5) | 0.047 (1) | |
C2 | 0.8195 (6) | 0.3754 (4) | 0.1431 (5) | 0.041 (1) | |
C3 | 0.3303 (6) | 0.4596 (4) | 0.3906 (5) | 0.043 (1) | |
C4 | 0.3369 (6) | 0.2561 (5) | 0.4378 (5) | 0.049 (1) | |
C5 | 0.2351 (7) | 0.2755 (5) | 0.5163 (5) | 0.054 (2) | |
C6 | 0.1814 (7) | 0.3907 (5) | 0.5242 (5) | 0.057 (2) | |
H4 | 0.3744 | 0.1801 | 0.4274 | 0.059* | |
H5 | 0.2029 | 0.2145 | 0.5626 | 0.065* | |
H6 | 0.1089 | 0.4048 | 0.5754 | 0.068* | |
H1n1 | 0.447 (5) | 0.336 (4) | 0.327 (4) | 0.04 (1)* | |
H3n1 | 0.441 (6) | 0.531 (5) | 0.278 (4) | 0.06 (2)* | |
H3n2 | 0.343 (7) | 0.615 (2) | 0.333 (6) | 0.07 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.056 (1) | 0.070 (1) | 0.095 (1) | 0.013 (1) | 0.026 (1) | 0.027 (1) |
Cl2 | 0.072 (1) | 0.049 (1) | 0.107 (1) | −0.023 (1) | 0.040 (1) | −0.009 (1) |
Cl3 | 0.069 (1) | 0.109 (1) | 0.052 (1) | −0.016 (1) | 0.022 (1) | −0.022 (1) |
O1 | 0.054 (2) | 0.038 (2) | 0.076 (3) | −0.006 (2) | 0.040 (2) | −0.003 (2) |
O2 | 0.091 (3) | 0.042 (2) | 0.122 (4) | 0.021 (2) | 0.071 (3) | 0.023 (2) |
N1 | 0.036 (2) | 0.040 (2) | 0.054 (3) | 0.004 (2) | 0.021 (2) | −0.004 (2) |
N2 | 0.055 (3) | 0.047 (3) | 0.065 (3) | 0.006 (2) | 0.028 (2) | −0.005 (2) |
N3 | 0.061 (3) | 0.040 (3) | 0.078 (4) | 0.014 (2) | 0.037 (3) | 0.010 (3) |
C1 | 0.047 (3) | 0.049 (3) | 0.047 (3) | 0.001 (3) | 0.018 (2) | 0.000 (2) |
C2 | 0.045 (3) | 0.033 (3) | 0.047 (3) | −0.003 (2) | 0.018 (2) | 0.001 (2) |
C3 | 0.039 (3) | 0.041 (3) | 0.050 (3) | 0.005 (2) | 0.012 (2) | −0.005 (2) |
C4 | 0.043 (3) | 0.040 (3) | 0.066 (4) | 0.002 (2) | 0.015 (3) | 0.000 (3) |
C5 | 0.058 (4) | 0.051 (3) | 0.059 (4) | 0.001 (3) | 0.025 (3) | 0.006 (3) |
C6 | 0.057 (4) | 0.063 (4) | 0.058 (4) | 0.004 (3) | 0.031 (3) | −0.005 (3) |
Cl1—C2 | 1.772 (5) | C1—C2 | 1.563 (7) |
Cl2—C2 | 1.753 (5) | C4—C5 | 1.360 (7) |
Cl3—C2 | 1.760 (5) | C5—C6 | 1.387 (8) |
O1—C1 | 1.250 (6) | N1—H1n1 | 0.85 (1) |
O2—C1 | 1.227 (6) | N3—H3n1 | 0.85 (1) |
N1—C4 | 1.344 (6) | N3—H3n2 | 0.85 (1) |
N1—C3 | 1.362 (6) | C4—H4 | 0.930 |
N2—C6 | 1.321 (7) | C5—H5 | 0.930 |
N2—C3 | 1.338 (6) | C6—H6 | 0.930 |
N3—C3 | 1.315 (7) | ||
C4—N1—C3 | 120.9 (4) | N1—C4—C5 | 119.3 (5) |
C6—N2—C3 | 116.7 (4) | C4—C5—C6 | 116.8 (5) |
O2—C1—O1 | 128.8 (5) | N2—C6—C5 | 124.6 (5) |
O2—C1—C2 | 116.4 (5) | C4—N1—H1n1 | 119 (3) |
O1—C1—C2 | 114.7 (4) | C3—N1—H1n1 | 120 (3) |
C1—C2—Cl2 | 112.8 (3) | C3—N3—H3n1 | 119 (4) |
C1—C2—Cl3 | 108.2 (3) | C3—N3—H3n2 | 119 (4) |
Cl2—C2—Cl3 | 110.1 (3) | H3n1—N3—H3n2 | 121 (6) |
C1—C2—Cl1 | 111.1 (3) | N1—C4—H4 | 120.3 |
Cl2—C2—Cl1 | 106.6 (3) | C5—C4—H4 | 120.3 |
Cl3—C2—Cl1 | 108.0 (3) | C4—C5—H5 | 121.6 |
N3—C3—N2 | 119.9 (5) | C6—C5—H5 | 121.6 |
N3—C3—N1 | 118.5 (5) | N2—C6—H6 | 117.7 |
N2—C3—N1 | 121.5 (5) | C5—C6—H6 | 117.7 |
O2—C1—C2—Cl2 | 21.1 (6) | C6—N2—C3—N1 | 2.4 (8) |
O1—C1—C2—Cl2 | −158.4 (4) | C4—N1—C3—N3 | 177.9 (5) |
O2—C1—C2—Cl3 | −100.9 (5) | C4—N1—C3—N2 | −2.9 (8) |
O1—C1—C2—Cl3 | 79.6 (5) | C3—N1—C4—C5 | 0.8 (8) |
O2—C1—C2—Cl1 | 140.7 (5) | N1—C4—C5—C6 | 1.6 (8) |
O1—C1—C2—Cl1 | −38.7 (6) | C3—N2—C6—C5 | 0.1 (9) |
C6—N2—C3—N3 | −178.5 (5) | C4—C5—C6—N2 | −2.1 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1n1···O1 | 0.85 (1) | 1.89 (1) | 2.733 (5) | 177 (5) |
N3—H3n1···O2 | 0.85 (1) | 1.95 (2) | 2.783 (6) | 166 (5) |
N3—H3n2···O1i | 0.85 (1) | 2.35 (4) | 3.026 (6) | 137 (5) |
C4—H4···O2ii | 0.93 | 2.42 | 3.271 (6) | 152 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C4H6N3+·C2Cl3O2− |
Mr | 258.49 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 8.468 (2), 11.297 (2), 10.957 (2) |
β (°) | 102.314 (3) |
V (Å3) | 1024.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.40 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5155, 1748, 1081 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.590 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.181, 1.04 |
No. of reflections | 1748 |
No. of parameters | 139 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.04, −0.51 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
X-ray structure | Geometry-optimized structure | |
Cl1-C2 | 1.772 (5) | 1.757 |
Cl2-C2 | 1.753 (5) | 1.754 |
Cl3-C2 | 1.760 (5) | 1.760 |
O1-C1 | 1.250 (6) | 1.263 |
O2-C1 | 1.227 (6) | 1.253 |
N1-C3 | 1.362 (6) | 1.404 |
N1-C4 | 1.344 (6) | 1.382 |
N2-C3 | 1.338 (6) | 1.402 |
N2-C6 | 1.321 (7) | 1.328 |
N3-C3 | 1.315 (7) | 1.351 |
C1-C2 | 1.563 (7) | 1.531 |
C4-C5 | 1.360 (7) | 1.374 |
C5-C6 | 1.387 (8) | 1.418 |
N1···O1 | 2.733 (5) | 2.704 |
N3···O2 | 2.783 (6) | 2.721 |
C4-N1-C3 | 120.9 (4) | 118.5 |
C6-N2-C3 | 116.7 (4) | 119.0 |
O1-C1-O2 | 128.8 (5) | 121.1 |
O1-C1-C2 | 114.7 (4) | 118.6 |
O2-C1-C2 | 116.4 (5) | 120.3 |
C1-C2-Cl1 | 111.1 (3) | 111.0 |
C1-C2-Cl2 | 112.8 (3) | 113.5 |
C1-C2-Cl3 | 108.2 (3) | 109.4 |
Cl1-C2-Cl2 | 106.6 (3) | 107.8 |
Cl1-C2-Cl3 | 108.0 (3) | 108.1 |
Cl2-C2-Cl3 | 110.1 (3) | 107.9 |
N1-C3-N2 | 121.5 (5) | 121.1 |
N1-C3-N3 | 118.5 (5) | 120.2 |
N2-C3-N3 | 119.9 (5) | 118.8 |
N1-C4-C5 | 119.3 (5) | 120.7 |
C4-C5-C6 | 116.8 (5) | 119.1 |
N2-C6-C5 | 124.6 (5) | 121.7 |
N1-H···O1 | 177 (5) | 180 |
N2-H···O2 | 166 (5) | 168 |
A number of carboxylic acids have been crystallographically documented as secondary-ammonium carboxylates; these compounds generally adopt dimeric hydrogen-bonded motifs (Ng et al., 2001). In the title 2-aminopyrimidin-1-ium carboxylate, the amino group forms a hydrogen bond with an oxygen atom of the carboxylate group, whose second oxygen atom is invoved in hydrogen bonding with the protonated nitrogen atom of the aromatic cation (Fig. 1). The ion-pairs are linked by a third, substantially weaker, hydrogen bond to furnish a helical chain that runs parallel to the b axis of the monoclinic cell (Fig. 2).
The calculated structure of the ion-pair that has been optimized at the PM3 level (Table 1) shows good agreement with the solid-state structure in the hydrogen-bonding interaction. However, the calculated structure has a delocalized carboxylate —COO− group, whereas the geometry of this group in the experimental structure is indicative of at least partial localization of single and double carbon–oxygen bonds.