organic compounds
4-(2-Methoxyphenyl)piperazin-1-ium 6-chloro-5-isopropyl-2,4-dioxopyrimidin-1-ide
aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, PO Box 2457, Riaydh 11451, Saudi Arabia, and bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: hfun.c@ksu.edu.sa
In the cation of the title salt, C11H17N2O+·C7H8ClN2O2−, the piperazine ring adopts a distorted chair conformation and contains a positively charged N atom with quaternary character. Its mean plane makes a dihedral angle of 42.36 (8)° with the phenyl ring of its 2-methoxyphenyl substituent. The 2,4-dioxopyrimidin-1-ide anion is generated by deprotonation of the N atom at the 1-position of the pyrimidinedione ring. Intramolecular C—H⋯O hydrogen bonds generate S(6) ring motifs in both the cation and the anion. In the crystal, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds are also observed, resulting in a two-dimensional network parallel to the ab plane. The crystal stability is further consolidated by weak C—H⋯π interactions.
CCDC reference: 984237
Related literature
For the chemotherapeutic activity of pyrimidine-2,4-dione derivatives, see: Ghoshal & Jacob (1997); Spacilova et al. (2007); Blokhina et al. (1972); Tanaka et al. (1995); El-Emam et al. (2004); Al-Turkistani et al. (2011). For the acidity of pyrimidine-2,4-dione derivatives, see: Kurinovich & Lee (2002); Jang et al. (2001); Nguyen et al. (1998). For the structures of other piperazinium salts, see: Craig et al. (2012); Dayananda et al. (2012); Fun et al. (2010). For reference bond lengths, see: Allen et al. (1987) and for hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
CCDC reference: 984237
10.1107/S1600536814002256/sj5388sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814002256/sj5388Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814002256/sj5388Isup3.cml
A mixture of 6-chloro-5-isopropyluracil (377 mg, 2.0 mmol), 1-(2-methoxyphenyl) piperazine (385 mg, 2.0 mmol) and anhydrous potassium carbonate (276 mg, 2.0 mmol), in ethanol (8 ml), was heated under reflux for 6 h. On cooling, the precipitate, thus formed was separated by filtration to yield 627 mg (91%) of 6-[4-(2-methoxyphenyl)-1-piperazinyl)]-5-isopropyluracil. The filtrate was concentrated by vacuum distillation to 5 ml and allowed to stand at room temperature overnight to yield 46 mg (6%) of the title salt (C18H25ClN4O3) as colourless plate-shaped crystals. M·P.: 517–519 K.
1H NMR (DMSO-d6, 500.13 MHz): δ 1.13 (d, 6H, CH3, J = 7.2 Hz), 2.53–2.56 (m, 1H, CH), 3.22–3.24 (m, 4H, Piperazine-H), 3.77 (s, 3H, OCH3), 3.42–3.45 (m, 4H, Piperazine-H), 6.78–7.02 (m, 4H, Ar—H), 8.02–8.14 (m, 2H, NH2), 10.88 (s, 1H, NH). 13C (DMSO-d6, 125.76 MHz): δ 19.50 (CH3), 26.90 (CH), 46.12, 49.86 (Piperazine-C), 56.80 (OCH3), 113.86, 119.12, 122.02, 122.98, 141.70, 148.28 (Ar—C), 123.90, 158.98, 162.82 (Pyrimidine-C),
The nitrogen-bound H-atoms were located in a difference Fourier map and were refined freely. Other H atoms were positioned geometrically (C=H 0.93–0.98 Å) and refined using a riding model with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms. A rotating group model was used for the methyl group.
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids. Intramolecular hydrogen bonds are drawn as dashed lines. | |
Fig. 2. Crystal packing of the title compound, showing the hydrogen bonding interactions as dashed lines. H-atoms not involved in the hydrogen bonding are omited for clarity. |
C11H17N2O+·C7H8ClN2O2− | F(000) = 808 |
Mr = 380.87 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 3769 reflections |
a = 8.9416 (2) Å | θ = 4.2–69.6° |
b = 10.5152 (3) Å | µ = 1.99 mm−1 |
c = 20.5626 (5) Å | T = 296 K |
β = 98.832 (1)° | Plate, colourless |
V = 1910.43 (8) Å3 | 0.81 × 0.13 × 0.05 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3531 independent reflections |
Radiation source: fine-focus sealed tube | 3204 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
φ and ω scans | θmax = 69.8°, θmin = 4.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.296, Tmax = 0.907 | k = −12→9 |
11481 measured reflections | l = −24→24 |
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0615P)2 + 0.5789P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
3531 reflections | Δρmax = 0.33 e Å−3 |
251 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0081 (5) |
C11H17N2O+·C7H8ClN2O2− | V = 1910.43 (8) Å3 |
Mr = 380.87 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 8.9416 (2) Å | µ = 1.99 mm−1 |
b = 10.5152 (3) Å | T = 296 K |
c = 20.5626 (5) Å | 0.81 × 0.13 × 0.05 mm |
β = 98.832 (1)° |
Bruker APEXII CCD diffractometer | 3531 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 3204 reflections with I > 2σ(I) |
Tmin = 0.296, Tmax = 0.907 | Rint = 0.033 |
11481 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.33 e Å−3 |
3531 reflections | Δρmin = −0.32 e Å−3 |
251 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 | ||
Cl1 | 0.50958 (5) | 0.52933 (5) | 0.21770 (2) | 0.05543 (19) | |
O2 | 0.20219 (13) | 0.51968 (11) | 0.00176 (5) | 0.0368 (3) | |
N4 | 0.34035 (14) | 0.51859 (13) | 0.10447 (7) | 0.0340 (3) | |
C14 | 0.20877 (17) | 0.51323 (14) | 0.06313 (7) | 0.0300 (3) | |
N3 | 0.07667 (15) | 0.50064 (14) | 0.08862 (7) | 0.0347 (3) | |
C15 | 0.0644 (2) | 0.49113 (17) | 0.15482 (8) | 0.0387 (4) | |
O3 | −0.06114 (16) | 0.47528 (17) | 0.17059 (7) | 0.0623 (4) | |
C12 | 0.33057 (18) | 0.51541 (15) | 0.16938 (8) | 0.0347 (3) | |
C13 | 0.2058 (2) | 0.50286 (16) | 0.19945 (8) | 0.0370 (4) | |
C16 | 0.2061 (2) | 0.49421 (19) | 0.27315 (9) | 0.0478 (4) | |
H16A | 0.3083 | 0.5163 | 0.2947 | 0.057* | |
C17 | 0.0969 (3) | 0.5878 (2) | 0.29765 (10) | 0.0591 (5) | |
H17A | 0.1235 | 0.6729 | 0.2871 | 0.089* | |
H17B | 0.1029 | 0.5796 | 0.3445 | 0.089* | |
H17C | −0.0044 | 0.5697 | 0.2768 | 0.089* | |
C18 | 0.1753 (4) | 0.3582 (2) | 0.29280 (12) | 0.0783 (8) | |
H18A | 0.2574 | 0.3045 | 0.2849 | 0.118* | |
H18B | 0.0829 | 0.3287 | 0.2672 | 0.118* | |
H18C | 0.1661 | 0.3556 | 0.3387 | 0.118* | |
O1 | 0.73479 (17) | 0.92628 (13) | 0.14090 (7) | 0.0524 (3) | |
N2 | 0.57634 (15) | 1.36876 (13) | 0.05996 (7) | 0.0347 (3) | |
N1 | 0.66629 (14) | 1.10889 (13) | 0.04804 (6) | 0.0343 (3) | |
C11 | 0.59845 (18) | 1.18107 (15) | −0.00956 (8) | 0.0359 (3) | |
H11A | 0.5429 | 1.1240 | −0.0416 | 0.043* | |
H11B | 0.6774 | 1.2216 | −0.0297 | 0.043* | |
C5 | 0.79466 (19) | 0.97928 (16) | −0.02689 (9) | 0.0393 (4) | |
H5A | 0.7690 | 1.0388 | −0.0602 | 0.047* | |
C10 | 0.49247 (17) | 1.28106 (16) | 0.01019 (9) | 0.0384 (4) | |
H10A | 0.4484 | 1.3291 | −0.0283 | 0.046* | |
H10B | 0.4109 | 1.2403 | 0.0285 | 0.046* | |
C8 | 0.75164 (18) | 1.19407 (16) | 0.09704 (8) | 0.0375 (4) | |
H8A | 0.8336 | 1.2332 | 0.0784 | 0.045* | |
H8B | 0.7956 | 1.1449 | 0.1351 | 0.045* | |
C3 | 0.9169 (2) | 0.78466 (17) | 0.00959 (10) | 0.0485 (5) | |
H3A | 0.9744 | 0.7141 | 0.0018 | 0.058* | |
C1 | 0.78835 (18) | 0.90656 (16) | 0.08317 (9) | 0.0395 (4) | |
C9 | 0.65130 (19) | 1.29640 (16) | 0.11833 (8) | 0.0374 (4) | |
H9A | 0.5750 | 1.2581 | 0.1409 | 0.045* | |
H9B | 0.7114 | 1.3539 | 0.1487 | 0.045* | |
C4 | 0.87617 (19) | 0.87161 (18) | −0.03948 (10) | 0.0457 (4) | |
H4A | 0.9028 | 0.8588 | −0.0810 | 0.055* | |
C6 | 0.75084 (17) | 0.99994 (15) | 0.03383 (8) | 0.0344 (3) | |
C2 | 0.8731 (2) | 0.80127 (17) | 0.07064 (10) | 0.0473 (4) | |
H2A | 0.9005 | 0.7414 | 0.1036 | 0.057* | |
C7 | 0.7453 (3) | 0.8242 (2) | 0.18654 (11) | 0.0666 (6) | |
H7A | 0.6991 | 0.8485 | 0.2238 | 0.100* | |
H7B | 0.8499 | 0.8039 | 0.2008 | 0.100* | |
H7C | 0.6942 | 0.7511 | 0.1658 | 0.100* | |
H2N2 | 0.646 (2) | 1.408 (2) | 0.0405 (10) | 0.040 (5)* | |
H1N2 | 0.511 (2) | 1.428 (2) | 0.0733 (10) | 0.043 (5)* | |
H1N3 | −0.006 (3) | 0.4964 (19) | 0.0606 (11) | 0.042 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0362 (3) | 0.0756 (4) | 0.0511 (3) | 0.0075 (2) | −0.00393 (18) | −0.0107 (2) |
O2 | 0.0322 (5) | 0.0468 (7) | 0.0329 (6) | −0.0035 (5) | 0.0101 (4) | 0.0021 (4) |
N4 | 0.0269 (6) | 0.0386 (7) | 0.0378 (7) | 0.0026 (5) | 0.0087 (5) | −0.0008 (5) |
C14 | 0.0288 (7) | 0.0278 (7) | 0.0351 (8) | 0.0002 (5) | 0.0105 (6) | 0.0000 (5) |
N3 | 0.0263 (7) | 0.0453 (8) | 0.0335 (7) | −0.0026 (5) | 0.0077 (6) | −0.0013 (5) |
C15 | 0.0376 (8) | 0.0440 (9) | 0.0371 (9) | −0.0034 (7) | 0.0142 (7) | −0.0024 (7) |
O3 | 0.0402 (7) | 0.1034 (12) | 0.0476 (8) | −0.0184 (7) | 0.0209 (6) | −0.0075 (7) |
C12 | 0.0319 (8) | 0.0338 (8) | 0.0379 (8) | 0.0042 (6) | 0.0038 (6) | −0.0034 (6) |
C13 | 0.0396 (9) | 0.0373 (8) | 0.0353 (8) | 0.0021 (6) | 0.0098 (7) | −0.0021 (6) |
C16 | 0.0551 (11) | 0.0542 (11) | 0.0350 (9) | 0.0060 (9) | 0.0101 (8) | −0.0027 (7) |
C17 | 0.0753 (14) | 0.0635 (13) | 0.0417 (10) | 0.0122 (11) | 0.0194 (9) | −0.0062 (9) |
C18 | 0.130 (2) | 0.0601 (14) | 0.0516 (12) | 0.0141 (15) | 0.0340 (14) | 0.0112 (10) |
O1 | 0.0662 (8) | 0.0449 (7) | 0.0478 (7) | 0.0088 (6) | 0.0147 (6) | 0.0087 (6) |
N2 | 0.0304 (6) | 0.0304 (7) | 0.0467 (8) | 0.0003 (5) | 0.0164 (6) | 0.0005 (5) |
N1 | 0.0326 (6) | 0.0310 (7) | 0.0383 (7) | 0.0024 (5) | 0.0029 (5) | −0.0018 (5) |
C11 | 0.0347 (7) | 0.0346 (8) | 0.0379 (8) | 0.0010 (6) | 0.0037 (6) | −0.0005 (6) |
C5 | 0.0348 (8) | 0.0388 (9) | 0.0442 (9) | −0.0001 (6) | 0.0054 (7) | −0.0022 (7) |
C10 | 0.0315 (8) | 0.0360 (8) | 0.0472 (9) | 0.0024 (6) | 0.0044 (7) | 0.0029 (7) |
C8 | 0.0348 (8) | 0.0355 (8) | 0.0410 (8) | 0.0023 (6) | 0.0019 (6) | −0.0025 (6) |
C3 | 0.0374 (8) | 0.0347 (9) | 0.0734 (13) | 0.0048 (7) | 0.0090 (8) | −0.0090 (8) |
C1 | 0.0364 (8) | 0.0345 (8) | 0.0464 (9) | −0.0008 (7) | 0.0025 (7) | −0.0001 (7) |
C9 | 0.0387 (8) | 0.0359 (8) | 0.0391 (8) | −0.0022 (7) | 0.0107 (7) | −0.0021 (6) |
C4 | 0.0378 (8) | 0.0449 (10) | 0.0558 (11) | 0.0000 (7) | 0.0112 (8) | −0.0123 (8) |
C6 | 0.0278 (7) | 0.0297 (8) | 0.0449 (9) | −0.0005 (6) | 0.0034 (6) | −0.0025 (6) |
C2 | 0.0440 (9) | 0.0333 (9) | 0.0627 (11) | 0.0052 (7) | 0.0020 (8) | 0.0044 (8) |
C7 | 0.0879 (16) | 0.0568 (13) | 0.0546 (12) | −0.0033 (12) | 0.0087 (11) | 0.0155 (10) |
Cl1—C12 | 1.7557 (17) | N1—C6 | 1.427 (2) |
O2—C14 | 1.2561 (19) | N1—C11 | 1.458 (2) |
N4—C14 | 1.343 (2) | N1—C8 | 1.471 (2) |
N4—C12 | 1.351 (2) | C11—C10 | 1.512 (2) |
C14—N3 | 1.3702 (19) | C11—H11A | 0.9700 |
N3—C15 | 1.386 (2) | C11—H11B | 0.9700 |
N3—H1N3 | 0.86 (3) | C5—C6 | 1.382 (2) |
C15—O3 | 1.226 (2) | C5—C4 | 1.392 (2) |
C15—C13 | 1.449 (3) | C5—H5A | 0.9300 |
C12—C13 | 1.362 (2) | C10—H10A | 0.9700 |
C13—C16 | 1.518 (2) | C10—H10B | 0.9700 |
C16—C18 | 1.523 (3) | C8—C9 | 1.508 (2) |
C16—C17 | 1.526 (3) | C8—H8A | 0.9700 |
C16—H16A | 0.9800 | C8—H8B | 0.9700 |
C17—H17A | 0.9600 | C3—C4 | 1.369 (3) |
C17—H17B | 0.9600 | C3—C2 | 1.383 (3) |
C17—H17C | 0.9600 | C3—H3A | 0.9300 |
C18—H18A | 0.9600 | C1—C2 | 1.388 (2) |
C18—H18B | 0.9600 | C1—C6 | 1.415 (2) |
C18—H18C | 0.9600 | C9—H9A | 0.9700 |
O1—C1 | 1.362 (2) | C9—H9B | 0.9700 |
O1—C7 | 1.419 (2) | C4—H4A | 0.9300 |
N2—C9 | 1.491 (2) | C2—H2A | 0.9300 |
N2—C10 | 1.491 (2) | C7—H7A | 0.9600 |
N2—H2N2 | 0.89 (2) | C7—H7B | 0.9600 |
N2—H1N2 | 0.93 (2) | C7—H7C | 0.9600 |
C14—N4—C12 | 116.17 (13) | C10—C11—H11A | 109.6 |
O2—C14—N4 | 122.35 (13) | N1—C11—H11B | 109.6 |
O2—C14—N3 | 118.64 (14) | C10—C11—H11B | 109.6 |
N4—C14—N3 | 119.00 (14) | H11A—C11—H11B | 108.2 |
C14—N3—C15 | 125.85 (15) | C6—C5—C4 | 121.67 (17) |
C14—N3—H1N3 | 116.7 (14) | C6—C5—H5A | 119.2 |
C15—N3—H1N3 | 117.5 (14) | C4—C5—H5A | 119.2 |
O3—C15—N3 | 118.90 (17) | N2—C10—C11 | 110.14 (13) |
O3—C15—C13 | 126.11 (16) | N2—C10—H10A | 109.6 |
N3—C15—C13 | 114.99 (14) | C11—C10—H10A | 109.6 |
N4—C12—C13 | 129.23 (16) | N2—C10—H10B | 109.6 |
N4—C12—Cl1 | 111.43 (12) | C11—C10—H10B | 109.6 |
C13—C12—Cl1 | 119.34 (13) | H10A—C10—H10B | 108.1 |
C12—C13—C15 | 114.63 (15) | N1—C8—C9 | 111.34 (13) |
C12—C13—C16 | 125.66 (17) | N1—C8—H8A | 109.4 |
C15—C13—C16 | 119.64 (15) | C9—C8—H8A | 109.4 |
C13—C16—C18 | 110.40 (16) | N1—C8—H8B | 109.4 |
C13—C16—C17 | 112.83 (16) | C9—C8—H8B | 109.4 |
C18—C16—C17 | 111.53 (18) | H8A—C8—H8B | 108.0 |
C13—C16—H16A | 107.3 | C4—C3—C2 | 120.27 (16) |
C18—C16—H16A | 107.3 | C4—C3—H3A | 119.9 |
C17—C16—H16A | 107.3 | C2—C3—H3A | 119.9 |
C16—C17—H17A | 109.5 | O1—C1—C2 | 123.92 (16) |
C16—C17—H17B | 109.5 | O1—C1—C6 | 116.29 (15) |
H17A—C17—H17B | 109.5 | C2—C1—C6 | 119.78 (16) |
C16—C17—H17C | 109.5 | N2—C9—C8 | 110.15 (13) |
H17A—C17—H17C | 109.5 | N2—C9—H9A | 109.6 |
H17B—C17—H17C | 109.5 | C8—C9—H9A | 109.6 |
C16—C18—H18A | 109.5 | N2—C9—H9B | 109.6 |
C16—C18—H18B | 109.5 | C8—C9—H9B | 109.6 |
H18A—C18—H18B | 109.5 | H9A—C9—H9B | 108.1 |
C16—C18—H18C | 109.5 | C3—C4—C5 | 119.60 (17) |
H18A—C18—H18C | 109.5 | C3—C4—H4A | 120.2 |
H18B—C18—H18C | 109.5 | C5—C4—H4A | 120.2 |
C1—O1—C7 | 117.67 (16) | C5—C6—C1 | 118.03 (15) |
C9—N2—C10 | 110.69 (13) | C5—C6—N1 | 122.93 (15) |
C9—N2—H2N2 | 109.9 (13) | C1—C6—N1 | 119.01 (15) |
C10—N2—H2N2 | 106.8 (13) | C3—C2—C1 | 120.56 (18) |
C9—N2—H1N2 | 109.4 (13) | C3—C2—H2A | 119.7 |
C10—N2—H1N2 | 110.2 (13) | C1—C2—H2A | 119.7 |
H2N2—N2—H1N2 | 109.8 (18) | O1—C7—H7A | 109.5 |
C6—N1—C11 | 114.77 (13) | O1—C7—H7B | 109.5 |
C6—N1—C8 | 113.17 (12) | H7A—C7—H7B | 109.5 |
C11—N1—C8 | 110.29 (13) | O1—C7—H7C | 109.5 |
N1—C11—C10 | 110.09 (13) | H7A—C7—H7C | 109.5 |
N1—C11—H11A | 109.6 | H7B—C7—H7C | 109.5 |
C12—N4—C14—O2 | 177.57 (14) | N1—C11—C10—N2 | 58.83 (17) |
C12—N4—C14—N3 | −2.2 (2) | C6—N1—C8—C9 | −171.18 (13) |
O2—C14—N3—C15 | 179.40 (15) | C11—N1—C8—C9 | 58.72 (17) |
N4—C14—N3—C15 | −0.8 (2) | C7—O1—C1—C2 | −10.5 (3) |
C14—N3—C15—O3 | −177.21 (17) | C7—O1—C1—C6 | 168.37 (18) |
C14—N3—C15—C13 | 3.5 (2) | C10—N2—C9—C8 | 55.06 (16) |
C14—N4—C12—C13 | 2.6 (2) | N1—C8—C9—N2 | −56.08 (18) |
C14—N4—C12—Cl1 | −177.68 (11) | C2—C3—C4—C5 | 2.2 (3) |
N4—C12—C13—C15 | 0.1 (3) | C6—C5—C4—C3 | −1.3 (3) |
Cl1—C12—C13—C15 | −179.54 (12) | C4—C5—C6—C1 | −1.4 (2) |
N4—C12—C13—C16 | 177.04 (17) | C4—C5—C6—N1 | −179.53 (15) |
Cl1—C12—C13—C16 | −2.6 (2) | O1—C1—C6—C5 | −175.88 (15) |
O3—C15—C13—C12 | 177.77 (18) | C2—C1—C6—C5 | 3.0 (2) |
N3—C15—C13—C12 | −3.0 (2) | O1—C1—C6—N1 | 2.4 (2) |
O3—C15—C13—C16 | 0.7 (3) | C2—C1—C6—N1 | −178.73 (15) |
N3—C15—C13—C16 | 179.89 (15) | C11—N1—C6—C5 | 14.0 (2) |
C12—C13—C16—C18 | −105.4 (2) | C8—N1—C6—C5 | −113.80 (17) |
C15—C13—C16—C18 | 71.4 (2) | C11—N1—C6—C1 | −164.14 (14) |
C12—C13—C16—C17 | 129.0 (2) | C8—N1—C6—C1 | 68.06 (18) |
C15—C13—C16—C17 | −54.2 (2) | C4—C3—C2—C1 | −0.5 (3) |
C6—N1—C11—C10 | 171.16 (13) | O1—C1—C2—C3 | 176.69 (17) |
C8—N1—C11—C10 | −59.59 (16) | C6—C1—C2—C3 | −2.1 (3) |
C9—N2—C10—C11 | −56.62 (16) |
Cg2 is centroid of the C1—C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N2···O2i | 0.892 (19) | 1.881 (19) | 2.7713 (18) | 176 (2) |
N2—H1N2···N4ii | 0.92 (2) | 1.987 (19) | 2.8923 (19) | 166.2 (18) |
N3—H1N3···O2iii | 0.87 (2) | 2.02 (3) | 2.8799 (18) | 177 (2) |
C8—H8B···O1 | 0.97 | 2.37 | 2.968 (2) | 119 |
C9—H9B···O3iv | 0.97 | 2.38 | 3.234 (2) | 146 |
C17—H17C···O3 | 0.96 | 2.38 | 3.015 (3) | 123 |
C10—H10B···Cg2i | 0.97 | 2.65 | 3.4041 (17) | 134 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y+1, z; (iii) −x, −y+1, −z; (iv) x+1, y+1, z. |
Cg2 is centroid of the C1—C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N2···O2i | 0.892 (19) | 1.881 (19) | 2.7713 (18) | 176 (2) |
N2—H1N2···N4ii | 0.92 (2) | 1.987 (19) | 2.8923 (19) | 166.2 (18) |
N3—H1N3···O2iii | 0.87 (2) | 2.02 (3) | 2.8799 (18) | 177 (2) |
C8—H8B···O1 | 0.9700 | 2.3700 | 2.968 (2) | 119.00 |
C9—H9B···O3iv | 0.9700 | 2.3800 | 3.234 (2) | 146.00 |
C17—H17C···O3 | 0.9600 | 2.3800 | 3.015 (3) | 123.00 |
C10—H10B···Cg2i | 0.9700 | 2.6500 | 3.4041 (17) | 134.00 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y+1, z; (iii) −x, −y+1, −z; (iv) x+1, y+1, z. |
Acknowledgements
The financial support of the Deanship of Scientific Research and the Research Center for Female Scientific and Medical Colleges, King Saud University, is greatly appreciated. CSCK thanks Universiti Sains Malaysia for a postdoctoral research fellowship.
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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.
Pyrimidine-2,4-diones (uracils) and their derivatives have been known from much earlier times for their diverse chemotherapeutic properties including anticancer (Ghoshal & Jacob, 1997; Spacilova et al., 2007; Blokhina et al., 1972), anti-HIV (Tanaka et al., 1995; El-Emam et al., 2004) and antibacterial activities (Al-Turkistani et al., 2011). The title piperazinium salt (I) was isolated as a minor by-product during the reaction of 6-chloro-5-isopropyluracil with 1-(2-methoxyphenyl)piperazine.
The asymmetric unit of (I) consists of a 4-(2-methoxyphenyl)piperazin-1-ium 6-chloro-5-isopropylpyrimidin-1-ide-2,4-dione cation-anion pair (Fig. 1). The 2,4-dioxopyrimidin-1-ide anion is generated by deprotonation of the N4 atom at the 1 position of the pyrimidine-dione ring (Kurinovich & Lee 2002; Jang et al., 2001; Nguyen et al., 1998). The six-membered piperazine ring (N1/C8/C9/N2/C10/C11) in the cation fragement adopts a slightly distorted chair conformation with puckering parameters: Q = 0.5774 (17) Å, θ = 177.86 (17) °, and φ = 129 (4) ° (Cremer & Pople, 1975) and contains a positively charged N atom (N2) with quaternary character. For an ideal chair configuration, θ has a value of 0 or 180°. The dihedral angle between the mean plane of the piperazine ring of the cation and the adjacent phenyl ring is 42.36 (8)°. Bond lengths (Allen et al., 1987) and angles in the title compound are within normal ranges and are comparable with those reported earlier (Craig et al. 2012; Dayananda et al., (2012); Fun et al., 2010). Intramolecular C17–H17C···O3 and C8–H8B···O1 hydrogen bonds generate S(6) ring motifs in both the cation and anion (Fig 1), while a strong intermolecular N2–H1N2···N4pyrimidine hydrogen bond links the two moieties. In the crystal, adjacent anionic species are interconnected via N2–H2N2···O2 and N3–H1N3···O2 hydrogen bonds (Table 1) with one bifurcated O acceptor atom on the anion resulting in R22(9) and R22(8) ring motifs (Bernstein et al., 1995) respectively. The crystal structure features an intermolecular C9–H9B···O3 hydrogen bond (Fig. 2) which links the entities into a two-dimensional structure. The crystal packing is further stabilized by a weak intermolecular C10–H10B···Cg2i interaction (Table 1) involving the centroid of the C1—C6 benzene ring.