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organic compounds
2-Amino-4-methyl-6-oxo-3,6-dihydropyrimidin-1-ium perchlorate–2-amino-6-methylpyrimidin-4(1H)-one–water (1/1/1)
aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, bChemistry Department and Centro di Strutturistica Diffrattometrica, University of Ferrara, Via L. Borsari 46, I-44121 Ferrara, Italy, and cYoungstown State University, Department of Chemistry, One University Plaza, Youngstown, Ohio 44555-3663, USA
*Correspondence e-mail: cherif_bennasr@yahoo.fr
In the title compound, C5H8N3O+·ClO4−·C5H7N3O·H2O, each perchlorate anion is paired with a protonated cationic 2-amino-6-methylpyrimidin-4(1H)-one and another non-protonated entity of the same organic pyrimidinone. The is stabilized by N—H⋯Oorg, N—H⋯Owater, N—H⋯OClO4, O—H⋯OClO4, N—H⋯N and C—H⋯OClO4 hydrogen bonds between the anions, organic entities and water molecules. Intermolecular π–π stacking interactions between neighbouring organic rings are observed with a face-to-face distance of 3.776 (2) Å, and O—H⋯O hydrogen bonds link the perchlorate anions and the water molecules into chains along the b-axis direction. The perchlorate anion and the interstitial water molecule are disordered over two mutually incompatible positions with a common occupancy ratio of 0.678 (16):0.322 (16).
Related literature
For general background to perchlorate salts with organic cations, see: Czarnecki et al. (1994); Czupinski et al. (2002
, 2006
). For enamine-imino resonance, see: Oueslati et al. (2007
). For π–π stacking interactions, see: Janiak (2000
).
Experimental
Crystal data
|
Data collection
|
Refinement
|
|
Data collection: Kappa CCD server software (Nonius, 1997); cell DENZO-SMN (Otwinowski & Minor, 1997
); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al.,1999
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: ORTEPIII (Burnett & Johnson, 1996
); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1983
, 1995
), WinGX (Farrugia, 1999
).
Supporting information
10.1107/S1600536811034106/bx2369sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811034106/bx2369Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811034106/bx2369Isup3.cml
An aqueous solution of Cu(ClO4)2 (1 mmol, 0.263 g) was added dropwise to a solution of 2-amino-4-hydroxy-6-methylpyrimidine (1 mmol, 0.125 g) in ethanol. The resultant mixture was evaporated at room temperature. Crystals of the title compound, which remained stable under normal conditions of temperature and humidity, were isolated after several days and subjected to X-ray
(yield 56%).Reflections (1 1 0), (1 0 0), (-1 0 2), (0 0 2), (0 1 1), (-1 1 1) and (-1 1 2) were obscured by the beamstop and were omitted from the
The oxygen atoms of the perchlorate ion were refined as disordered over two mutually exclusive sets of positions with a refined occupancy ratio of 0.678 (16) to 0.322 (16) for the two orientations. Associated with the perchlorate disorder is disorder of a water molecule, which is distributed over two positions in the same ratio as the anions. All Cl—O bond distances and O···O distances within each disordered moiety were restrained to be eadch the same within a standard deviation of 0.02 Å. C—H and N—H hydrogen atoms were placed in calculated positions with C—H distances of 0.93 and 0.96 Å and N—H distances of 0.86 Å. The the water hydrogen atom postitions were refined with O—H distance restraints of 0.82 (2) Å and H···H distance restraints within each water molecule of 1.35 (2) Å. Uiso(H) values of all H atoms were constrained to 1.2 (amine, C—H) or 1.5 (CH3, O—H) times Ueq of the respective parent atom.Data collection: Kappa CCD server software (Nonius, 1997); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al.,1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PARST (Nardelli, 1983, 1995), WinGX (Farrugia, 1999).C5H8N3O+·ClO4−·C5H7N3O·H2O | F(000) = 768 |
Mr = 368.75 | Dx = 1.503 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7792 reflections |
a = 10.3669 (3) Å | θ = 2.0–30.0° |
b = 10.4342 (3) Å | µ = 0.28 mm−1 |
c = 15.0780 (5) Å | T = 295 K |
β = 92.751 (2)° | Prismatic, colourless |
V = 1629.11 (9) Å3 | 0.30 × 0.15 × 0.12 mm |
Z = 4 |
Nonius Kappa CCD diffractometer | 2765 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 30.1°, θmin = 3.9° |
ϕ scans and ω scans | h = −14→14 |
7792 measured reflections | k = −13→14 |
4739 independent reflections | l = −21→21 |
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)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.184 | w = 1/[σ2(Fo2) + (0.1048P)2 + 0.0794P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
4739 reflections | Δρmax = 0.38 e Å−3 |
279 parameters | Δρmin = −0.47 e Å−3 |
64 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (6) |
C5H8N3O+·ClO4−·C5H7N3O·H2O | V = 1629.11 (9) Å3 |
Mr = 368.75 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.3669 (3) Å | µ = 0.28 mm−1 |
b = 10.4342 (3) Å | T = 295 K |
c = 15.0780 (5) Å | 0.30 × 0.15 × 0.12 mm |
β = 92.751 (2)° |
Nonius Kappa CCD diffractometer | 2765 reflections with I > 2σ(I) |
7792 measured reflections | Rint = 0.027 |
4739 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | 64 restraints |
wR(F2) = 0.184 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.38 e Å−3 |
4739 reflections | Δρmin = −0.47 e Å−3 |
279 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 | Occ. (<1) | |
O5 | 0.98648 (14) | 0.24064 (14) | 0.41381 (8) | 0.0481 (4) | |
N1 | 0.98287 (15) | 0.26652 (14) | 0.56248 (9) | 0.0370 (4) | |
H1 | 1.0315 | 0.3329 | 0.5589 | 0.044* | |
N2 | 0.87048 (15) | 0.12750 (14) | 0.64911 (9) | 0.0386 (4) | |
H2 | 0.8495 | 0.1022 | 0.7007 | 0.046* | |
N3 | 0.98691 (18) | 0.29455 (16) | 0.71393 (10) | 0.0489 (4) | |
H3A | 0.9635 | 0.2717 | 0.7656 | 0.059* | |
H3B | 1.0363 | 0.3600 | 0.7086 | 0.059* | |
C1 | 0.94722 (17) | 0.22960 (16) | 0.64336 (11) | 0.0357 (4) | |
C2 | 0.94490 (18) | 0.20263 (17) | 0.48438 (11) | 0.0384 (4) | |
C3 | 0.85884 (19) | 0.09806 (19) | 0.49410 (12) | 0.0452 (5) | |
H3 | 0.8263 | 0.0545 | 0.4441 | 0.054* | |
C4 | 0.82387 (18) | 0.06148 (17) | 0.57560 (12) | 0.0407 (4) | |
C5 | 0.7351 (2) | −0.0476 (2) | 0.59327 (15) | 0.0579 (6) | |
H5A | 0.7149 | −0.0929 | 0.5390 | 0.087* | |
H5B | 0.6569 | −0.0151 | 0.6165 | 0.087* | |
H5C | 0.7763 | −0.1048 | 0.6357 | 0.087* | |
Cl1 | 0.32526 (6) | 0.13475 (6) | 0.68097 (4) | 0.0630 (2) | |
O1 | 0.2053 (11) | 0.0786 (17) | 0.6977 (12) | 0.098 (5) | 0.322 (16) |
O2 | 0.308 (2) | 0.2428 (18) | 0.6303 (18) | 0.206 (11) | 0.322 (16) |
O3 | 0.3952 (12) | 0.0439 (15) | 0.6352 (11) | 0.109 (4) | 0.322 (16) |
O4 | 0.3901 (18) | 0.161 (3) | 0.7605 (10) | 0.163 (9) | 0.322 (16) |
O1' | 0.2309 (8) | 0.0465 (8) | 0.7085 (4) | 0.100 (2) | 0.678 (16) |
O2' | 0.2776 (6) | 0.2018 (6) | 0.6061 (3) | 0.0944 (18) | 0.678 (16) |
O3' | 0.4372 (9) | 0.0699 (10) | 0.6589 (6) | 0.133 (3) | 0.678 (16) |
O4' | 0.3540 (11) | 0.2203 (8) | 0.7502 (5) | 0.125 (3) | 0.678 (16) |
O1WA | 0.559 (2) | 0.3844 (18) | 0.6839 (13) | 0.097 (5) | 0.322 (16) |
H1WA | 0.543 (12) | 0.457 (6) | 0.702 (10) | 0.146* | 0.322 (16) |
H2WA | 0.493 (7) | 0.342 (10) | 0.676 (11) | 0.146* | 0.322 (16) |
O1WB | 0.6081 (9) | 0.3409 (9) | 0.6947 (5) | 0.089 (2) | 0.678 (16) |
H1WB | 0.620 (6) | 0.387 (5) | 0.739 (3) | 0.134* | 0.678 (16) |
H2WB | 0.549 (5) | 0.292 (5) | 0.703 (4) | 0.134* | 0.678 (16) |
O6 | 0.85711 (15) | 0.49047 (14) | 0.30449 (8) | 0.0523 (4) | |
N4 | 0.84030 (15) | 0.52739 (15) | 0.45051 (9) | 0.0389 (4) | |
N5 | 0.68242 (16) | 0.41812 (16) | 0.52703 (11) | 0.0481 (4) | |
H5 | 0.6483 | 0.4026 | 0.5768 | 0.058* | |
N6 | 0.82368 (19) | 0.55766 (18) | 0.59950 (11) | 0.0582 (5) | |
H6A | 0.8880 | 0.6097 | 0.5994 | 0.070* | |
H6B | 0.7866 | 0.5420 | 0.6482 | 0.070* | |
C6 | 0.78157 (18) | 0.50162 (17) | 0.52456 (12) | 0.0410 (4) | |
C7 | 0.79858 (19) | 0.46791 (18) | 0.37411 (12) | 0.0417 (4) | |
C8 | 0.6914 (2) | 0.3822 (2) | 0.37529 (14) | 0.0538 (5) | |
H8 | 0.6605 | 0.3434 | 0.3230 | 0.065* | |
C9 | 0.6351 (2) | 0.3576 (2) | 0.45156 (14) | 0.0508 (5) | |
C10 | 0.5254 (3) | 0.2665 (3) | 0.46219 (18) | 0.0743 (7) | |
H10A | 0.4962 | 0.2344 | 0.4050 | 0.111* | |
H10B | 0.4558 | 0.3103 | 0.4890 | 0.111* | |
H10C | 0.5538 | 0.1963 | 0.4994 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O5 | 0.0660 (9) | 0.0544 (8) | 0.0244 (6) | −0.0120 (7) | 0.0079 (6) | −0.0008 (5) |
N1 | 0.0466 (9) | 0.0390 (8) | 0.0257 (7) | −0.0069 (6) | 0.0037 (6) | −0.0001 (6) |
N2 | 0.0459 (9) | 0.0422 (8) | 0.0281 (7) | −0.0032 (6) | 0.0066 (6) | 0.0057 (6) |
N3 | 0.0691 (11) | 0.0525 (9) | 0.0256 (7) | −0.0143 (8) | 0.0069 (7) | 0.0002 (7) |
C1 | 0.0412 (10) | 0.0392 (9) | 0.0269 (8) | 0.0025 (7) | 0.0041 (7) | 0.0035 (7) |
C2 | 0.0454 (10) | 0.0436 (9) | 0.0264 (8) | −0.0001 (8) | 0.0039 (7) | −0.0011 (7) |
C3 | 0.0527 (12) | 0.0493 (10) | 0.0335 (9) | −0.0091 (9) | 0.0005 (8) | −0.0039 (8) |
C4 | 0.0415 (10) | 0.0420 (9) | 0.0388 (9) | −0.0020 (8) | 0.0030 (8) | 0.0032 (8) |
C5 | 0.0631 (14) | 0.0588 (13) | 0.0523 (12) | −0.0214 (11) | 0.0065 (10) | 0.0013 (10) |
Cl1 | 0.0656 (4) | 0.0782 (4) | 0.0458 (3) | −0.0041 (3) | 0.0098 (3) | −0.0022 (3) |
O1 | 0.053 (5) | 0.129 (10) | 0.116 (11) | −0.008 (5) | 0.037 (5) | −0.013 (7) |
O2 | 0.25 (2) | 0.100 (10) | 0.28 (2) | 0.081 (11) | 0.129 (16) | 0.109 (12) |
O3 | 0.064 (6) | 0.143 (8) | 0.120 (8) | 0.019 (5) | 0.000 (5) | −0.057 (7) |
O4 | 0.125 (11) | 0.28 (3) | 0.081 (7) | −0.063 (14) | −0.040 (7) | −0.040 (12) |
O1' | 0.147 (6) | 0.103 (4) | 0.050 (2) | −0.066 (4) | 0.023 (3) | −0.003 (2) |
O2' | 0.111 (3) | 0.114 (4) | 0.058 (2) | 0.019 (3) | 0.005 (2) | 0.025 (2) |
O3' | 0.090 (5) | 0.173 (7) | 0.137 (6) | 0.060 (5) | 0.026 (4) | 0.024 (4) |
O4' | 0.145 (6) | 0.139 (5) | 0.091 (4) | −0.052 (4) | 0.010 (3) | −0.053 (3) |
O1WA | 0.117 (12) | 0.095 (10) | 0.083 (9) | −0.046 (8) | 0.044 (9) | −0.025 (7) |
O1WB | 0.108 (5) | 0.096 (5) | 0.063 (2) | −0.035 (3) | 0.008 (3) | 0.013 (3) |
O6 | 0.0736 (10) | 0.0537 (8) | 0.0303 (7) | −0.0154 (7) | 0.0105 (7) | −0.0060 (6) |
N4 | 0.0467 (9) | 0.0413 (8) | 0.0292 (7) | −0.0049 (7) | 0.0057 (6) | −0.0030 (6) |
N5 | 0.0461 (9) | 0.0579 (10) | 0.0412 (8) | −0.0084 (8) | 0.0100 (7) | 0.0035 (7) |
N6 | 0.0717 (12) | 0.0730 (12) | 0.0312 (8) | −0.0255 (10) | 0.0160 (8) | −0.0090 (8) |
C6 | 0.0465 (10) | 0.0425 (9) | 0.0346 (9) | −0.0010 (8) | 0.0076 (8) | −0.0003 (7) |
C7 | 0.0500 (11) | 0.0432 (10) | 0.0321 (8) | −0.0030 (8) | 0.0029 (8) | −0.0029 (7) |
C8 | 0.0576 (13) | 0.0617 (12) | 0.0415 (10) | −0.0159 (10) | −0.0029 (9) | −0.0029 (9) |
C9 | 0.0449 (11) | 0.0559 (11) | 0.0513 (11) | −0.0096 (9) | −0.0010 (9) | 0.0020 (10) |
C10 | 0.0633 (16) | 0.0858 (18) | 0.0738 (16) | −0.0298 (13) | 0.0041 (13) | 0.0066 (14) |
O5—C2 | 1.233 (2) | Cl1—O1 | 1.408 (10) |
N1—C1 | 1.347 (2) | Cl1—O1' | 1.419 (5) |
N1—C2 | 1.393 (2) | O1WA—H1WA | 0.82 (2) |
N1—H1 | 0.8600 | O1WA—H2WA | 0.82 (2) |
N2—C1 | 1.335 (2) | O1WB—H1WB | 0.831 (19) |
N2—C4 | 1.373 (2) | O1WB—H2WB | 0.82 (2) |
N2—H2 | 0.8600 | O6—C7 | 1.260 (2) |
N3—C1 | 1.311 (2) | N4—C6 | 1.325 (2) |
N3—H3A | 0.8600 | N4—C7 | 1.361 (2) |
N3—H3B | 0.8600 | N5—C6 | 1.349 (2) |
C2—C3 | 1.421 (3) | N5—C9 | 1.371 (3) |
C3—C4 | 1.353 (2) | N5—H5 | 0.8600 |
C3—H3 | 0.9300 | N6—C6 | 1.327 (2) |
C4—C5 | 1.496 (3) | N6—H6A | 0.8600 |
C5—H5A | 0.9600 | N6—H6B | 0.8600 |
C5—H5B | 0.9600 | C7—C8 | 1.427 (3) |
C5—H5C | 0.9600 | C8—C9 | 1.339 (3) |
Cl1—O2 | 1.369 (10) | C8—H8 | 0.9300 |
Cl1—O4 | 1.373 (10) | C9—C10 | 1.497 (3) |
Cl1—O4' | 1.395 (5) | C10—H10A | 0.9600 |
Cl1—O3 | 1.396 (10) | C10—H10B | 0.9600 |
Cl1—O3' | 1.397 (6) | C10—H10C | 0.9600 |
Cl1—O2' | 1.398 (4) | ||
C1—N1—C2 | 123.33 (15) | O2—Cl1—O1 | 110.4 (9) |
C1—N1—H1 | 118.3 | O4—Cl1—O1 | 109.0 (9) |
C2—N1—H1 | 118.3 | O3—Cl1—O1 | 106.8 (8) |
C1—N2—C4 | 122.40 (14) | O4'—Cl1—O1' | 108.8 (4) |
C1—N2—H2 | 118.8 | O3'—Cl1—O1' | 110.3 (4) |
C4—N2—H2 | 118.8 | O2'—Cl1—O1' | 109.8 (4) |
C1—N3—H3A | 120.0 | H1WA—O1WA—H2WA | 111 (4) |
C1—N3—H3B | 120.0 | H1WB—O1WB—H2WB | 109 (3) |
H3A—N3—H3B | 120.0 | C6—N4—C7 | 118.73 (15) |
N3—C1—N2 | 121.65 (15) | C6—N5—C9 | 121.13 (16) |
N3—C1—N1 | 119.85 (16) | C6—N5—H5 | 119.4 |
N2—C1—N1 | 118.50 (15) | C9—N5—H5 | 119.4 |
O5—C2—N1 | 118.64 (16) | C6—N6—H6A | 120.0 |
O5—C2—C3 | 125.68 (16) | C6—N6—H6B | 120.0 |
N1—C2—C3 | 115.68 (15) | H6A—N6—H6B | 120.0 |
C4—C3—C2 | 120.48 (17) | N4—C6—N6 | 118.84 (17) |
C4—C3—H3 | 119.8 | N4—C6—N5 | 122.41 (16) |
C2—C3—H3 | 119.8 | N6—C6—N5 | 118.74 (16) |
C3—C4—N2 | 119.50 (16) | O6—C7—N4 | 118.29 (16) |
C3—C4—C5 | 124.79 (18) | O6—C7—C8 | 122.28 (17) |
N2—C4—C5 | 115.70 (16) | N4—C7—C8 | 119.43 (16) |
C4—C5—H5A | 109.5 | C9—C8—C7 | 120.16 (19) |
C4—C5—H5B | 109.5 | C9—C8—H8 | 119.9 |
H5A—C5—H5B | 109.5 | C7—C8—H8 | 119.9 |
C4—C5—H5C | 109.5 | C8—C9—N5 | 118.10 (18) |
H5A—C5—H5C | 109.5 | C8—C9—C10 | 125.3 (2) |
H5B—C5—H5C | 109.5 | N5—C9—C10 | 116.56 (19) |
O2—Cl1—O4 | 111.9 (9) | C9—C10—H10A | 109.5 |
O2—Cl1—O3 | 109.9 (9) | C9—C10—H10B | 109.5 |
O4—Cl1—O3 | 108.7 (8) | H10A—C10—H10B | 109.5 |
O4'—Cl1—O3' | 109.8 (5) | C9—C10—H10C | 109.5 |
O4'—Cl1—O2' | 109.8 (4) | H10A—C10—H10C | 109.5 |
O3'—Cl1—O2' | 108.4 (4) | H10B—C10—H10C | 109.5 |
C4—N2—C1—N3 | 177.34 (17) | C7—N4—C6—N6 | 178.73 (18) |
C4—N2—C1—N1 | −1.9 (3) | C7—N4—C6—N5 | 0.4 (3) |
C2—N1—C1—N3 | 179.95 (17) | C9—N5—C6—N4 | −1.6 (3) |
C2—N1—C1—N2 | −0.8 (3) | C9—N5—C6—N6 | 179.98 (19) |
C1—N1—C2—O5 | −177.23 (18) | C6—N4—C7—O6 | −178.20 (18) |
C1—N1—C2—C3 | 3.4 (3) | C6—N4—C7—C8 | 1.5 (3) |
O5—C2—C3—C4 | 177.18 (19) | O6—C7—C8—C9 | 177.6 (2) |
N1—C2—C3—C4 | −3.4 (3) | N4—C7—C8—C9 | −2.1 (3) |
C2—C3—C4—N2 | 1.1 (3) | C7—C8—C9—N5 | 0.9 (3) |
C2—C3—C4—C5 | −179.47 (19) | C7—C8—C9—C10 | −177.8 (2) |
C1—N2—C4—C3 | 1.8 (3) | C6—N5—C9—C8 | 1.0 (3) |
C1—N2—C4—C5 | −177.75 (17) | C6—N5—C9—C10 | 179.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1WA—H2WA···O2 | 0.82 (2) | 2.26 (6) | 3.07 (4) | 169 (16) |
C5—H5B···O3′ | 0.96 | 2.55 | 3.509 (6) | 173 |
N5—H5···O1WB | 0.86 | 1.95 | 2.797 (8) | 166 |
O1WB—H2WB···O4′ | 0.82 (2) | 2.30 (4) | 3.071 (14) | 159 (6) |
N1—H1···N4i | 0.86 | 1.98 | 2.839 (2) | 174 |
N3—H3B···O6i | 0.86 | 1.93 | 2.787 (2) | 178 |
N6—H6A···O5i | 0.86 | 2.05 | 2.895 (2) | 168 |
N2—H2···O6ii | 0.86 | 1.84 | 2.6560 (18) | 158 |
N3—H3A···O5ii | 0.86 | 2.24 | 3.0363 (18) | 154 |
N6—H6B···O1iii | 0.86 | 2.35 | 3.095 (17) | 145 |
C3—H3···O1iv | 0.93 | 2.56 | 3.466 (17) | 166 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C5H8N3O+·ClO4−·C5H7N3O·H2O |
Mr | 368.75 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.3669 (3), 10.4342 (3), 15.0780 (5) |
β (°) | 92.751 (2) |
V (Å3) | 1629.11 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.30 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7792, 4739, 2765 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.184, 1.02 |
No. of reflections | 4739 |
No. of parameters | 279 |
No. of restraints | 64 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.47 |
Computer programs: Kappa CCD server software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al.,1999), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 2008), PARST (Nardelli, 1983, 1995), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1WA—H2WA···O2 | 0.82 (2) | 2.26 (6) | 3.07 (4) | 169 (16) |
C5—H5B···O3' | 0.96 | 2.55 | 3.509 (6) | 173.0 |
N5—H5···O1WB | 0.86 | 1.95 | 2.797 (8) | 166.0 |
O1WB—H2WB···O4' | 0.82 (2) | 2.30 (4) | 3.071 (14) | 159 (6) |
N1—H1···N4i | 0.86 | 1.98 | 2.839 (2) | 173.7 |
N3—H3B···O6i | 0.86 | 1.93 | 2.787 (2) | 178.4 |
N6—H6A···O5i | 0.86 | 2.05 | 2.895 (2) | 167.8 |
N2—H2···O6ii | 0.86 | 1.84 | 2.6560 (18) | 158.4 |
N3—H3A···O5ii | 0.86 | 2.24 | 3.0363 (18) | 153.9 |
N6—H6B···O1iii | 0.86 | 2.35 | 3.095 (17) | 144.6 |
C3—H3···O1iv | 0.93 | 2.56 | 3.466 (17) | 166.1 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, −y, −z+1. |
Acknowledgements
The authors acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Perchlorate salts containing organic cations have been studied extensively in recent years owing to some of their interesting properties such as e.g. ferroelectric and dielectric behaviour (Czarnecki et al., 1994; Czupinski et al., 2002; Czupinski et al., 2006). Here, we report the synthesis and the crystal structure of one such compound, (C5H8N3O)(C5H7N3O)ClO4.H2O.
The crystal structure of the title compound (Fig.1) contains one perchlorate anion, one water molecule, and two 2-amino-6-methylpyrimidin-4(1H)-one molecules. One of these molecules is protonated at the nitrogen atom of the six membered ring, thus formally changing the molecule into a 2-amino-4-methyl-6-oxo-3,6-dihydropyrimidin-1-ium cation. The atomic arrangement of (C5H8N3O)(C5H7N3O)ClO4.H2O can be divided into an organic and an inorganic part. The inorganic section is composed of chains of [ClO4]- tetrahedra and water molecules that extend along the b axis direction, held together by Owater—H···O(ClO4) hydrogen bonds. Two such chains cross the unit cell at z = (2n +1)/4 and x = 0.5 (Fig. 2, Table 1). The organic groups are located between these chains and connect to them through N—H···Owater, N—H···O(ClO4) and C—H···O(ClO4) hydrogen bonds to form a three dimensional infinite network (Fig. 3, Table 1). Of the hydrogen bonds, one is bifurcted: O1WA—H2WA···(O2, O4) (Fig. 2, Table 1). The organic entities are associated with each other via N—H···Oorg and N—H···N hydrogen bonds (Fig. 3, Table 1). Intermolecular π-π stacking interactions between neighbouring organic rings are observed with a face-to-face distance of 3.776 (2) Å, less than 3.8 Å, the maximum regarded as relevant for π-π interactions (Janiak, 2000).
The C—N bond distances of the NH2 groups, N3—C1 and N6—C6, are 1.311 (2) and 1.327 (2) Å, respectively, which is short for a C—N single bond, but still not quite as contracted as one would expect for a fully established C=N double bond. These bond length features are consistent with an imino resonance form as it is commonly found for C—N single bonds involving sp2 hybridized C and N atoms (Oueslati et al., 2007). The distance values of C2—O5 [1.233 (2) Å] and C7—O6 [1.260 (2) Å] clearly indicate two C=O double bonds. This confirms that the first step of the formation of the title compound consists in the tautomerization of the starting material 2-amino-4-hydroxy-6-methylpyrimidine into 2-amino-6-methylpyrimidin-4(1H)-one.