organic compounds
of ethyl 4-(2-fluorophenyl)-6-methyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylate
aDepartment of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore 560 001, Karnataka, India
*Correspondence e-mail: noorsb@rediffmail.com
The title compound, C14H15FN2O2S, crystallizes with two molecules in the In each molecule, the pyrimidine ring adopts a sofa conformation with the sp3-hybridized C atom forming the flap and the fluoro-substituted ring in an axial position. In the crystal, molecules are linked via N—H⋯S hydrogen bonds, forming chains of R22(8) rings along [100]. In one independent molecule, an intramolecular C—H⋯O hydrogen bond is observed.
Keywords: crystal structure; ester; pyrimidine; hydrogen bonding; 3,4-dihydropyrimidin-2(1H)-one; therapeutic properties; pharmacological properties.
CCDC reference: 1418668
1. Related literature
For the therapeutic and pharmacological properties of 3,4-dihydropyrimidin-2(1H)-ones, see: Kappe (2000); Hurst & Hull (1961); Mayer et al. (1999); Atwal et al. (1991). For their applications in calcium-channel modulators, see: Kappe (1998); Jauk et al. (2000); Krishnamurthy & Begum (2015). For the bioactivity of organo–fluorine compounds, see: Hermann et al. (2003); Ulrich (2004). For examples of fluorine-directed crystal packing, see: Prasanna & Guru Row (2001). For related structures, see: Qin et al. (2006); Krishnamurthy & Begum (2015). For hydrogen-bond graph-set notation, see: Bernstein et al. (1995).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: SMART (Bruker, 1998); cell SMART; data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), CAMERON (Watkin et al., 1996) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 1418668
10.1107/S2056989015015145/lh5781sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015015145/lh5781Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015015145/lh5781Isup3.cml
The title compound was synthesized by the reaction of 2-fluorobenzaldehyde (1.24 g, 10 mmol), ethylacetoacetate (1.52 g, 12 mmol) and thiourea (1.14 g, 15 mmol) in 15 ml ethanol was refluxed for 6 h in the presence of concentrated hydrochloric acid as a catalyst. The reaction was monitored with TLC and the reaction medium was quenched in ice cold water. The precipitate obtained was filtered and dried. The compound was recrystallized from ethanol solvent by slow evaporation method, yielding colorless blocks suitable for X-ray diffraction studies (yield 76%; m.p. 485 K).
The H atoms were placed in calculated positions in a riding-model approximation with N—H = 0.86° A; C—H = 0.93° A, 0.96 ° A and 0.97 ° A for aromatic, methyl and methylene H-atoms respectively, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(C) for other hydrogen atoms.
Data collection: SMART (Bruker, 1998); cell
SMART (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), CAMERON (Watkin et al., 1996) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius. | |
Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines. |
C14H15FN2O2S | Z = 4 |
Mr = 294.34 | F(000) = 616 |
Triclinic, P1 | Dx = 1.290 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9298 (6) Å | Cell parameters from 5328 reflections |
b = 11.5870 (8) Å | θ = 2.4–25.0° |
c = 15.7459 (11) Å | µ = 0.23 mm−1 |
α = 100.940 (2)° | T = 100 K |
β = 104.804 (2)° | Block, colourless |
γ = 98.153 (2)° | 0.18 × 0.16 × 0.16 mm |
V = 1515.11 (18) Å3 |
Bruker SMART APEX CCD diffractometer | 5328 independent reflections |
Radiation source: fine-focus sealed tube | 3389 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→10 |
Tmin = 0.960, Tmax = 0.965 | k = −13→13 |
17808 measured reflections | l = −18→18 |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.228 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.1269P)2 + 1.4728P] where P = (Fo2 + 2Fc2)/3 |
5328 reflections | (Δ/σ)max = 0.001 |
365 parameters | Δρmax = 1.04 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
C14H15FN2O2S | γ = 98.153 (2)° |
Mr = 294.34 | V = 1515.11 (18) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.9298 (6) Å | Mo Kα radiation |
b = 11.5870 (8) Å | µ = 0.23 mm−1 |
c = 15.7459 (11) Å | T = 100 K |
α = 100.940 (2)° | 0.18 × 0.16 × 0.16 mm |
β = 104.804 (2)° |
Bruker SMART APEX CCD diffractometer | 5328 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 3389 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.965 | Rint = 0.039 |
17808 measured reflections |
R[F2 > 2σ(F2)] = 0.075 | 0 restraints |
wR(F2) = 0.228 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.04 e Å−3 |
5328 reflections | Δρmin = −0.35 e Å−3 |
365 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | ||
S1 | 0.86288 (13) | 0.90033 (10) | 0.07601 (7) | 0.0522 (3) | |
O1 | 0.6733 (4) | 0.6314 (3) | −0.3693 (2) | 0.0743 (10) | |
O2 | 0.4450 (4) | 0.6240 (3) | −0.33627 (19) | 0.0701 (10) | |
N1 | 0.8792 (4) | 0.8058 (3) | −0.0880 (2) | 0.0489 (9) | |
H1 | 0.9822 | 0.8229 | −0.0631 | 0.059* | |
N2 | 0.6330 (4) | 0.7993 (3) | −0.0734 (2) | 0.0414 (8) | |
H2 | 0.5717 | 0.8312 | −0.0439 | 0.050* | |
F1 | 0.2317 (4) | 0.6093 (4) | −0.2084 (3) | 0.1226 (14) | |
C1 | 0.9490 (6) | 0.7543 (5) | −0.2257 (3) | 0.0738 (15) | |
H1A | 0.9492 | 0.6715 | −0.2544 | 0.111* | |
H1B | 1.0519 | 0.7900 | −0.1810 | 0.111* | |
H1C | 0.9294 | 0.8010 | −0.2717 | 0.111* | |
C2 | 0.7856 (5) | 0.8314 (3) | −0.0339 (3) | 0.0412 (9) | |
C3 | 0.6001 (5) | 0.6538 (4) | −0.3149 (3) | 0.0499 (10) | |
C4 | 0.5536 (4) | 0.7162 (3) | −0.1611 (2) | 0.0382 (9) | |
H4 | 0.4611 | 0.7476 | −0.1922 | 0.046* | |
C5 | 0.6672 (5) | 0.7122 (3) | −0.2183 (3) | 0.0415 (9) | |
C6 | 0.8224 (5) | 0.7548 (4) | −0.1798 (3) | 0.0460 (10) | |
C7 | 0.3610 (7) | 0.5580 (6) | −0.4281 (3) | 0.0891 (19) | |
H7A | 0.3593 | 0.6128 | −0.4694 | 0.107* | |
H7B | 0.4162 | 0.4939 | −0.4471 | 0.107* | |
C8 | 0.2083 (10) | 0.5082 (10) | −0.4334 (5) | 0.172 (5) | |
H8A | 0.2091 | 0.4715 | −0.3822 | 0.258* | |
H8B | 0.1620 | 0.4467 | −0.4901 | 0.258* | |
H8C | 0.1453 | 0.5708 | −0.4319 | 0.258* | |
C9 | 0.4933 (5) | 0.5941 (4) | −0.1489 (3) | 0.0455 (10) | |
C10 | 0.5973 (7) | 0.5272 (4) | −0.1092 (3) | 0.0641 (13) | |
H10 | 0.7080 | 0.5584 | −0.0905 | 0.077* | |
C11 | 0.5406 (10) | 0.4154 (5) | −0.0968 (4) | 0.091 (2) | |
H11 | 0.6121 | 0.3698 | −0.0706 | 0.109* | |
C12 | 0.3822 (15) | 0.3718 (6) | −0.1225 (5) | 0.121 (3) | |
H12 | 0.3439 | 0.2959 | −0.1130 | 0.145* | |
C13 | 0.2769 (9) | 0.4347 (7) | −0.1617 (5) | 0.103 (2) | |
H13 | 0.1664 | 0.4031 | −0.1807 | 0.123* | |
C14 | 0.3357 (6) | 0.5445 (5) | −0.1726 (3) | 0.0669 (13) | |
S1' | 0.31495 (13) | 0.84530 (11) | −0.00790 (7) | 0.0544 (4) | |
O1' | 0.6197 (5) | 1.1437 (4) | 0.4307 (3) | 0.0940 (13) | |
O2' | 0.3597 (4) | 1.0906 (3) | 0.4089 (2) | 0.0683 (9) | |
N1' | 0.5140 (4) | 0.9516 (3) | 0.1541 (2) | 0.0490 (9) | |
H1' | 0.5889 | 0.9363 | 0.1291 | 0.059* | |
N2' | 0.2541 (4) | 0.9254 (3) | 0.1455 (2) | 0.0463 (8) | |
H2' | 0.1559 | 0.9156 | 0.1118 | 0.056* | |
F1' | 0.0344 (4) | 0.9094 (4) | 0.3206 (3) | 0.1074 (12) | |
C1' | 0.7322 (5) | 1.0702 (5) | 0.2784 (3) | 0.0692 (14) | |
H1'1 | 0.7651 | 1.0866 | 0.3446 | 0.104* | |
H1'2 | 0.7528 | 1.1453 | 0.2595 | 0.104* | |
H1'3 | 0.7921 | 1.0141 | 0.2544 | 0.104* | |
C2' | 0.3619 (5) | 0.9103 (3) | 0.1028 (3) | 0.0428 (9) | |
C3' | 0.4889 (6) | 1.0926 (4) | 0.3814 (3) | 0.0603 (12) | |
C4' | 0.2823 (5) | 0.9565 (4) | 0.2428 (3) | 0.0448 (10) | |
H4' | 0.2094 | 1.0105 | 0.2567 | 0.054* | |
C5' | 0.4504 (5) | 1.0246 (3) | 0.2879 (3) | 0.0454 (10) | |
C6' | 0.5595 (5) | 1.0163 (4) | 0.2430 (3) | 0.0475 (10) | |
C7' | 0.3799 (8) | 1.1522 (5) | 0.5011 (4) | 0.0890 (18) | |
H7'1 | 0.4179 | 1.2393 | 0.5096 | 0.107* | |
H7'2 | 0.4591 | 1.1219 | 0.5431 | 0.107* | |
C8' | 0.2281 (11) | 1.1309 (9) | 0.5198 (5) | 0.144 (3) | |
H8'1 | 0.1539 | 1.1693 | 0.4828 | 0.217* | |
H8'2 | 0.2423 | 1.1647 | 0.5839 | 0.217* | |
H8'3 | 0.1862 | 1.0443 | 0.5052 | 0.217* | |
C9' | 0.2458 (5) | 0.8451 (4) | 0.2768 (3) | 0.0467 (10) | |
C10' | 0.3336 (6) | 0.7567 (4) | 0.2711 (3) | 0.0623 (13) | |
H10' | 0.4194 | 0.7666 | 0.2460 | 0.075* | |
C11' | 0.2998 (8) | 0.6546 (5) | 0.3007 (4) | 0.0861 (18) | |
H11' | 0.3602 | 0.5939 | 0.2946 | 0.103* | |
C12' | 0.1789 (9) | 0.6404 (6) | 0.3392 (4) | 0.091 (2) | |
H12' | 0.1561 | 0.5704 | 0.3604 | 0.109* | |
C13' | 0.0928 (8) | 0.7260 (7) | 0.3468 (4) | 0.0926 (19) | |
H13' | 0.0103 | 0.7176 | 0.3745 | 0.111* | |
C14' | 0.1248 (6) | 0.8256 (5) | 0.3142 (3) | 0.0675 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0422 (6) | 0.0611 (7) | 0.0453 (6) | 0.0011 (5) | 0.0124 (5) | 0.0006 (5) |
O1 | 0.076 (2) | 0.100 (3) | 0.0456 (18) | 0.012 (2) | 0.0265 (18) | 0.0051 (17) |
O2 | 0.053 (2) | 0.103 (3) | 0.0393 (17) | −0.0082 (18) | 0.0078 (14) | 0.0048 (16) |
N1 | 0.0334 (18) | 0.065 (2) | 0.044 (2) | 0.0023 (16) | 0.0144 (15) | 0.0047 (17) |
N2 | 0.0351 (18) | 0.0450 (18) | 0.0419 (18) | 0.0053 (15) | 0.0147 (15) | 0.0024 (15) |
F1 | 0.057 (2) | 0.161 (4) | 0.132 (3) | −0.004 (2) | 0.017 (2) | 0.025 (3) |
C1 | 0.057 (3) | 0.099 (4) | 0.063 (3) | −0.001 (3) | 0.034 (3) | 0.003 (3) |
C2 | 0.039 (2) | 0.037 (2) | 0.047 (2) | 0.0044 (17) | 0.0133 (19) | 0.0094 (18) |
C3 | 0.057 (3) | 0.049 (2) | 0.045 (2) | 0.005 (2) | 0.016 (2) | 0.017 (2) |
C4 | 0.034 (2) | 0.041 (2) | 0.039 (2) | 0.0074 (17) | 0.0101 (17) | 0.0083 (17) |
C5 | 0.048 (2) | 0.040 (2) | 0.038 (2) | 0.0046 (18) | 0.0154 (18) | 0.0136 (17) |
C6 | 0.047 (2) | 0.046 (2) | 0.046 (2) | 0.0057 (19) | 0.020 (2) | 0.0094 (19) |
C7 | 0.076 (4) | 0.117 (5) | 0.044 (3) | −0.023 (3) | 0.001 (3) | 0.001 (3) |
C8 | 0.102 (6) | 0.268 (12) | 0.072 (5) | −0.073 (7) | 0.008 (4) | −0.030 (6) |
C9 | 0.052 (2) | 0.045 (2) | 0.037 (2) | 0.000 (2) | 0.0194 (19) | 0.0025 (18) |
C10 | 0.097 (4) | 0.047 (3) | 0.059 (3) | 0.016 (3) | 0.037 (3) | 0.016 (2) |
C11 | 0.158 (7) | 0.054 (3) | 0.086 (4) | 0.026 (4) | 0.068 (4) | 0.027 (3) |
C12 | 0.216 (10) | 0.057 (4) | 0.095 (5) | −0.029 (5) | 0.098 (6) | 0.001 (4) |
C13 | 0.107 (5) | 0.087 (5) | 0.096 (5) | −0.045 (4) | 0.051 (4) | −0.003 (4) |
C14 | 0.055 (3) | 0.075 (3) | 0.063 (3) | −0.008 (3) | 0.022 (3) | 0.006 (3) |
S1' | 0.0444 (6) | 0.0736 (8) | 0.0449 (6) | 0.0117 (5) | 0.0137 (5) | 0.0122 (5) |
O1' | 0.076 (3) | 0.107 (3) | 0.067 (2) | −0.007 (2) | 0.008 (2) | −0.017 (2) |
O2' | 0.077 (2) | 0.071 (2) | 0.0534 (19) | 0.0092 (18) | 0.0289 (17) | −0.0019 (16) |
N1' | 0.0341 (18) | 0.062 (2) | 0.049 (2) | 0.0068 (16) | 0.0149 (16) | 0.0067 (17) |
N2' | 0.0359 (18) | 0.066 (2) | 0.0409 (19) | 0.0151 (16) | 0.0118 (15) | 0.0167 (16) |
F1' | 0.083 (2) | 0.135 (3) | 0.138 (3) | 0.034 (2) | 0.074 (2) | 0.047 (2) |
C1' | 0.042 (3) | 0.084 (3) | 0.070 (3) | −0.003 (2) | 0.014 (2) | 0.005 (3) |
C2' | 0.038 (2) | 0.045 (2) | 0.050 (2) | 0.0109 (18) | 0.0160 (19) | 0.0165 (19) |
C3' | 0.069 (3) | 0.050 (3) | 0.060 (3) | 0.010 (2) | 0.018 (3) | 0.011 (2) |
C4' | 0.041 (2) | 0.051 (2) | 0.046 (2) | 0.0133 (19) | 0.0185 (19) | 0.0086 (19) |
C5' | 0.048 (2) | 0.042 (2) | 0.045 (2) | 0.0080 (19) | 0.012 (2) | 0.0090 (18) |
C6' | 0.042 (2) | 0.046 (2) | 0.051 (3) | 0.0055 (19) | 0.012 (2) | 0.010 (2) |
C7' | 0.134 (6) | 0.077 (4) | 0.057 (3) | 0.021 (4) | 0.039 (4) | 0.004 (3) |
C8' | 0.153 (7) | 0.189 (8) | 0.105 (6) | 0.029 (6) | 0.092 (6) | −0.004 (5) |
C9' | 0.045 (2) | 0.052 (2) | 0.038 (2) | 0.003 (2) | 0.0100 (19) | 0.0067 (19) |
C10' | 0.082 (3) | 0.049 (3) | 0.057 (3) | 0.007 (2) | 0.025 (3) | 0.012 (2) |
C11' | 0.126 (5) | 0.054 (3) | 0.069 (4) | 0.016 (3) | 0.014 (4) | 0.013 (3) |
C12' | 0.121 (5) | 0.074 (4) | 0.065 (4) | −0.022 (4) | 0.022 (4) | 0.024 (3) |
C13' | 0.094 (5) | 0.102 (5) | 0.083 (4) | −0.014 (4) | 0.040 (4) | 0.031 (4) |
C14' | 0.061 (3) | 0.076 (3) | 0.064 (3) | 0.000 (3) | 0.027 (3) | 0.012 (3) |
S1—C2 | 1.679 (4) | S1'—C2' | 1.679 (4) |
O1—C3 | 1.216 (5) | O1'—C3' | 1.218 (6) |
O2—C3 | 1.316 (5) | O2'—C3' | 1.330 (6) |
O2—C7 | 1.450 (5) | O2'—C7' | 1.443 (6) |
N1—C2 | 1.360 (5) | N1'—C2' | 1.354 (5) |
N1—C6 | 1.382 (5) | N1'—C6' | 1.383 (5) |
N1—H1 | 0.8800 | N1'—H1' | 0.8800 |
N2—C2 | 1.311 (5) | N2'—C2' | 1.321 (5) |
N2—C4 | 1.463 (5) | N2'—C4' | 1.452 (5) |
N2—H2 | 0.8800 | N2'—H2' | 0.8800 |
F1—C14 | 1.355 (6) | F1'—C14' | 1.354 (6) |
C1—C6 | 1.490 (6) | C1'—C6' | 1.496 (6) |
C1—H1A | 0.9800 | C1'—H1'1 | 0.9800 |
C1—H1B | 0.9800 | C1'—H1'2 | 0.9800 |
C1—H1C | 0.9800 | C1'—H1'3 | 0.9800 |
C3—C5 | 1.469 (6) | C3'—C5' | 1.459 (6) |
C4—C9 | 1.506 (5) | C4'—C5' | 1.512 (6) |
C4—C5 | 1.518 (5) | C4'—C9' | 1.513 (6) |
C4—H4 | 1.0000 | C4'—H4' | 1.0000 |
C5—C6 | 1.340 (6) | C5'—C6' | 1.346 (6) |
C7—C8 | 1.378 (9) | C7'—C8' | 1.456 (9) |
C7—H7A | 0.9900 | C7'—H7'1 | 0.9900 |
C7—H7B | 0.9900 | C7'—H7'2 | 0.9900 |
C8—H8A | 0.9800 | C8'—H8'1 | 0.9800 |
C8—H8B | 0.9800 | C8'—H8'2 | 0.9800 |
C8—H8C | 0.9800 | C8'—H8'3 | 0.9800 |
C9—C14 | 1.368 (6) | C9'—C14' | 1.368 (6) |
C9—C10 | 1.394 (6) | C9'—C10' | 1.378 (6) |
C10—C11 | 1.391 (7) | C10'—C11' | 1.375 (7) |
C10—H10 | 0.9500 | C10'—H10' | 0.9500 |
C11—C12 | 1.359 (11) | C11'—C12' | 1.371 (9) |
C11—H11 | 0.9500 | C11'—H11' | 0.9500 |
C12—C13 | 1.366 (11) | C12'—C13' | 1.345 (9) |
C12—H12 | 0.9500 | C12'—H12' | 0.9500 |
C13—C14 | 1.365 (8) | C13'—C14' | 1.373 (8) |
C13—H13 | 0.9500 | C13'—H13' | 0.9500 |
C3—O2—C7 | 117.6 (4) | C3'—O2'—C7' | 117.2 (4) |
C2—N1—C6 | 124.0 (3) | C2'—N1'—C6' | 124.3 (3) |
C2—N1—H1 | 118.0 | C2'—N1'—H1' | 117.8 |
C6—N1—H1 | 118.0 | C6'—N1'—H1' | 117.8 |
C2—N2—C4 | 127.1 (3) | C2'—N2'—C4' | 126.1 (3) |
C2—N2—H2 | 116.5 | C2'—N2'—H2' | 117.0 |
C4—N2—H2 | 116.5 | C4'—N2'—H2' | 117.0 |
C6—C1—H1A | 109.5 | C6'—C1'—H1'1 | 109.5 |
C6—C1—H1B | 109.5 | C6'—C1'—H1'2 | 109.5 |
H1A—C1—H1B | 109.5 | H1'1—C1'—H1'2 | 109.5 |
C6—C1—H1C | 109.5 | C6'—C1'—H1'3 | 109.5 |
H1A—C1—H1C | 109.5 | H1'1—C1'—H1'3 | 109.5 |
H1B—C1—H1C | 109.5 | H1'2—C1'—H1'3 | 109.5 |
N2—C2—N1 | 115.6 (3) | N2'—C2'—N1' | 115.6 (4) |
N2—C2—S1 | 122.9 (3) | N2'—C2'—S1' | 122.6 (3) |
N1—C2—S1 | 121.5 (3) | N1'—C2'—S1' | 121.8 (3) |
O1—C3—O2 | 122.7 (4) | O1'—C3'—O2' | 122.5 (5) |
O1—C3—C5 | 126.7 (4) | O1'—C3'—C5' | 126.7 (5) |
O2—C3—C5 | 110.6 (4) | O2'—C3'—C5' | 110.8 (4) |
N2—C4—C9 | 110.5 (3) | N2'—C4'—C5' | 109.6 (3) |
N2—C4—C5 | 108.9 (3) | N2'—C4'—C9' | 110.5 (3) |
C9—C4—C5 | 112.3 (3) | C5'—C4'—C9' | 112.3 (3) |
N2—C4—H4 | 108.3 | N2'—C4'—H4' | 108.1 |
C9—C4—H4 | 108.3 | C5'—C4'—H4' | 108.1 |
C5—C4—H4 | 108.3 | C9'—C4'—H4' | 108.1 |
C6—C5—C3 | 122.6 (4) | C6'—C5'—C3' | 122.6 (4) |
C6—C5—C4 | 120.3 (3) | C6'—C5'—C4' | 119.7 (4) |
C3—C5—C4 | 117.0 (3) | C3'—C5'—C4' | 117.7 (4) |
C5—C6—N1 | 120.0 (4) | C5'—C6'—N1' | 119.4 (4) |
C5—C6—C1 | 126.9 (4) | C5'—C6'—C1' | 127.2 (4) |
N1—C6—C1 | 113.1 (4) | N1'—C6'—C1' | 113.4 (4) |
C8—C7—O2 | 110.1 (5) | O2'—C7'—C8' | 108.5 (6) |
C8—C7—H7A | 109.6 | O2'—C7'—H7'1 | 110.0 |
O2—C7—H7A | 109.6 | C8'—C7'—H7'1 | 110.0 |
C8—C7—H7B | 109.6 | O2'—C7'—H7'2 | 110.0 |
O2—C7—H7B | 109.6 | C8'—C7'—H7'2 | 110.0 |
H7A—C7—H7B | 108.2 | H7'1—C7'—H7'2 | 108.4 |
C7—C8—H8A | 109.5 | C7'—C8'—H8'1 | 109.5 |
C7—C8—H8B | 109.5 | C7'—C8'—H8'2 | 109.5 |
H8A—C8—H8B | 109.5 | H8'1—C8'—H8'2 | 109.5 |
C7—C8—H8C | 109.5 | C7'—C8'—H8'3 | 109.5 |
H8A—C8—H8C | 109.5 | H8'1—C8'—H8'3 | 109.5 |
H8B—C8—H8C | 109.5 | H8'2—C8'—H8'3 | 109.5 |
C14—C9—C10 | 116.4 (4) | C14'—C9'—C10' | 116.2 (4) |
C14—C9—C4 | 122.6 (4) | C14'—C9'—C4' | 122.6 (4) |
C10—C9—C4 | 120.9 (4) | C10'—C9'—C4' | 121.2 (4) |
C11—C10—C9 | 120.6 (6) | C11'—C10'—C9' | 121.6 (5) |
C11—C10—H10 | 119.7 | C11'—C10'—H10' | 119.2 |
C9—C10—H10 | 119.7 | C9'—C10'—H10' | 119.2 |
C12—C11—C10 | 119.6 (7) | C12'—C11'—C10' | 119.9 (6) |
C12—C11—H11 | 120.2 | C12'—C11'—H11' | 120.1 |
C10—C11—H11 | 120.2 | C10'—C11'—H11' | 120.1 |
C11—C12—C13 | 121.3 (6) | C13'—C12'—C11' | 119.8 (5) |
C11—C12—H12 | 119.3 | C13'—C12'—H12' | 120.1 |
C13—C12—H12 | 119.3 | C11'—C12'—H12' | 120.1 |
C14—C13—C12 | 117.8 (7) | C12'—C13'—C14' | 119.5 (6) |
C14—C13—H13 | 121.1 | C12'—C13'—H13' | 120.2 |
C12—C13—H13 | 121.1 | C14'—C13'—H13' | 120.2 |
F1—C14—C13 | 118.1 (6) | F1'—C14'—C9' | 118.4 (4) |
F1—C14—C9 | 117.7 (4) | F1'—C14'—C13' | 118.6 (5) |
C13—C14—C9 | 124.2 (6) | C9'—C14'—C13' | 123.0 (6) |
C4—N2—C2—N1 | 15.5 (6) | C4'—N2'—C2'—N1' | −14.4 (6) |
C4—N2—C2—S1 | −164.9 (3) | C4'—N2'—C2'—S1' | 166.1 (3) |
C6—N1—C2—N2 | 3.0 (6) | C6'—N1'—C2'—N2' | −6.2 (6) |
C6—N1—C2—S1 | −176.6 (3) | C6'—N1'—C2'—S1' | 173.3 (3) |
C7—O2—C3—O1 | 2.2 (7) | C7'—O2'—C3'—O1' | −0.1 (7) |
C7—O2—C3—C5 | −176.0 (4) | C7'—O2'—C3'—C5' | 178.7 (4) |
C2—N2—C4—C9 | 99.7 (4) | C2'—N2'—C4'—C5' | 26.5 (5) |
C2—N2—C4—C5 | −24.1 (5) | C2'—N2'—C4'—C9' | −97.8 (4) |
O1—C3—C5—C6 | 4.1 (7) | O1'—C3'—C5'—C6' | −3.7 (7) |
O2—C3—C5—C6 | −177.8 (4) | O2'—C3'—C5'—C6' | 177.5 (4) |
O1—C3—C5—C4 | −172.3 (4) | O1'—C3'—C5'—C4' | 173.1 (5) |
O2—C3—C5—C4 | 5.9 (5) | O2'—C3'—C5'—C4' | −5.6 (5) |
N2—C4—C5—C6 | 16.0 (5) | N2'—C4'—C5'—C6' | −20.0 (5) |
C9—C4—C5—C6 | −106.7 (4) | C9'—C4'—C5'—C6' | 103.1 (4) |
N2—C4—C5—C3 | −167.6 (3) | N2'—C4'—C5'—C3' | 163.0 (3) |
C9—C4—C5—C3 | 69.7 (4) | C9'—C4'—C5'—C3' | −73.8 (5) |
C3—C5—C6—N1 | −178.2 (4) | C3'—C5'—C6'—N1' | −179.1 (4) |
C4—C5—C6—N1 | −2.0 (6) | C4'—C5'—C6'—N1' | 4.1 (6) |
C3—C5—C6—C1 | 1.9 (7) | C3'—C5'—C6'—C1' | 1.1 (7) |
C4—C5—C6—C1 | 178.1 (4) | C4'—C5'—C6'—C1' | −175.7 (4) |
C2—N1—C6—C5 | −9.2 (6) | C2'—N1'—C6'—C5' | 10.9 (6) |
C2—N1—C6—C1 | 170.7 (4) | C2'—N1'—C6'—C1' | −169.3 (4) |
C3—O2—C7—C8 | 164.9 (7) | C3'—O2'—C7'—C8' | −175.2 (5) |
N2—C4—C9—C14 | 114.6 (4) | N2'—C4'—C9'—C14' | −114.4 (4) |
C5—C4—C9—C14 | −123.6 (4) | C5'—C4'—C9'—C14' | 123.0 (4) |
N2—C4—C9—C10 | −63.1 (5) | N2'—C4'—C9'—C10' | 65.2 (5) |
C5—C4—C9—C10 | 58.8 (5) | C5'—C4'—C9'—C10' | −57.5 (5) |
C14—C9—C10—C11 | 1.1 (6) | C14'—C9'—C10'—C11' | 0.5 (7) |
C4—C9—C10—C11 | 179.0 (4) | C4'—C9'—C10'—C11' | −179.1 (4) |
C9—C10—C11—C12 | −0.9 (8) | C9'—C10'—C11'—C12' | −1.7 (8) |
C10—C11—C12—C13 | 1.0 (10) | C10'—C11'—C12'—C13' | 0.7 (9) |
C11—C12—C13—C14 | −1.4 (10) | C11'—C12'—C13'—C14' | 1.4 (9) |
C12—C13—C14—F1 | −177.6 (6) | C10'—C9'—C14'—F1' | −179.5 (4) |
C12—C13—C14—C9 | 1.7 (9) | C4'—C9'—C14'—F1' | 0.1 (7) |
C10—C9—C14—F1 | 177.8 (4) | C10'—C9'—C14'—C13' | 1.7 (7) |
C4—C9—C14—F1 | 0.0 (6) | C4'—C9'—C14'—C13' | −178.7 (5) |
C10—C9—C14—C13 | −1.6 (7) | C12'—C13'—C14'—F1' | 178.5 (5) |
C4—C9—C14—C13 | −179.3 (5) | C12'—C13'—C14'—C9' | −2.7 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1′i | 0.88 | 2.83 | 3.703 (4) | 170 |
N1′—H1′···S1 | 0.88 | 2.84 | 3.711 (4) | 171 |
N2—H2···S1′ | 0.88 | 2.52 | 3.337 (4) | 155 |
N2′—H2′···S1ii | 0.88 | 2.50 | 3.335 (5) | 158 |
C1′—H1′1···O1′ | 0.98 | 2.14 | 2.861 (6) | 129 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1'i | 0.88 | 2.83 | 3.703 (4) | 170 |
N1'—H1'···S1 | 0.88 | 2.84 | 3.711 (4) | 171 |
N2—H2···S1' | 0.88 | 2.52 | 3.337 (4) | 155 |
N2'—H2'···S1ii | 0.88 | 2.50 | 3.335 (5) | 158 |
C1'—H1'1···O1' | 0.98 | 2.14 | 2.861 (6) | 129 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
Acknowledgements
MSK thanks for the University Grants Commission (UGC), India, for the UGC–BSR Meritorious 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.
The Biginelli reaction is a three-component condensation of ethyl acetoacetate, benzaldehyde and urea for the synthesis of 3,4-dihydropyrimidine-2(1H) -ones (abbreviated as DHPMs). DHPMs have recently emerged as important target molecules because of their therapeutic and pharmacological properties (Kappe, 2000), such as antiviral (Hurst & Hull, 1961), antimitotic (Mayer et al., 1999), anticarcinogenic and antihypertensive (Atwal et al., 1991). They are also noteworthy as calcium channel modulators (Kappe, 1998; Jauk et al., 2000). In addition, compounds that contain fluorine have special bioactivity, e.g. flumioxazin is a widely used herbicide (Hermann et al., 2003; Ulrich, 2004). Guru Row and co-workers have extensively studied the structural property of fluorine and they have presented several elegant examples of fluorine directed crystal packing (Prasanna & Guru Row, 2001). Herein, we report the crystal structure of the title compound.
The asymmetric unit of the title compound is shown in Fig. 1. There are two indpendent molecules in the asymmetric unit. The bond lengths and bond angles are in good agreement with the corresponding bond distances and angles reported in closely related structures (Qin et al., 2006; Krishnamurthy & Begum, 2015). In each molecule, the pyrimidine ring adopts a sofa conformation with the sp3 hybridized carbon atom [C4 and C4'] forming the flap and the fluoro-substituted ring in an axial position. The carbonyl group of the exocyclic ester at C5 and C5' adopts a cis orientation with respect to the C5═C6 and C5'═C6 double bond. The fluoro-substituted benzene ring adopts an syn periplanar conformation with respect to the C4—H4 and C4'—H4' bonds. In the crystal, molecules are linked via N—H···S hydrogen bonds forming chains of R22(8) rings (Bernstein et al., 1995) along [100] (Fig. 2). In one independent molecule an intramolecular C—H···O hydrogen bond is observed.