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organic compounds
Ethyl 4-(furan-2-yl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate
aCollege of Chemistry and Chemical Technology, Binzhou University, Binzhou 256600, Shandong, People's Republic of China
*Correspondence e-mail: whybzxy@163.com
The 12H14N2O4, contains two independent molecules. In one independent molecule, the furanyl fragment is rotationally disordered between two orientations in a 0.625 (6):0.375 (6) ratio. In the crystal, intermolecular pyrimidine–pyrimidinone N—H⋯O hydrogen bonds link the molecules into centrosymmetric tetramers, which are further associated into ribbons extending in [010] via weak intermolecular pyrimidine–carboxyl N—H⋯O hydrogen bonds.
of the title compound, CRelated literature
The Biginelli reaction is the most important procedure in the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones, see: Biginelli (1893). For related structures, see: Nizam Mohideen et al. (2008
); Qing-Fang et al. (2007
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536810040456/cv2771sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040456/cv2771Isup2.hkl
A mixture of ethylacetoacetate (0.5 mol), furfural (0.5 mol) and urea (0.6 mol) was refluxed in 50.0 ml of ethanol for 2.0 hrs. The reaction completion was monitored through thin layer
and the reaction mixture was quenched in ice cold water. The precipitate obtained was filtered, dried and crystallized from methanol to obtain the title compound.All H atoms were placed in geometrically idealized positions (N—H 0.86 and C—H = 0.93–0.97 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2U-1.5eq(C, N). Atoms C4, C5, C6, O2 were treated as disordered between two positions, with refined occupancies of 0.375 (6) and 0.625 (6).
Biginelli reaction is a well known multicomponent reaction involving a one-pot cyclocondensation of an aldehyde, β-ketoester and urea/thiourea. It is the most important procedure in the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones (Biginelli, 1893). Herewith we report the of the title compound, (I), obtained by the three-component reaction of furfuraldehyde, acetoacetate and urea.
In (I) (Fig. 1), the dihydropyrimidinone rings adopt flattened boat conformation. The
contains two independent molecules. In one independent molecule, the furanyl fragment is rotationally disordered in a ratio 0.625 (6):0.375 (6). The bond lengths an angles are normal and comparable to the values observed in similar compounds (Nizam Mohideen et al., 2008; Qing-Fang et al., 2007) The dihedral angles between the furan rings (C3—C6/O2, C15—C18/O6) and the mean planes of the dihydropyrimidinone rings (N1/C1/N2/C9/C8, N3/C13/N4/C21/C20) unit in two independent molecules are 88.79 (4) ° and 86.73 (2)°, respectively, indicating that the furan rings and the dihydropyrimidinone rings are nearly perpendicular.In the
intermolecular N—H···Opyrimidinone hydrogen bonds (Table 1) link the molecules into centrosymmetric tetramers. Tetramers are further associated into ribbons extended in direction [010] via the weak intermolecular N—H···Ocarboxyl hydrogen bonds (Table 1).Biginelli reaction is the most important procedure in the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones, see: Biginelli et al. (1893). For related structures, see: Nizam Mohideen et al. (2008); Qing-Fang et al. (2007).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). ![]() | Fig. 1. The content of asymmetric unit of the title compound showing the atomic numbering scheme and 30% probability displacement ellipsoids. Only major components of the disordered atoms are shown. |
C12H14N2O4 | F(000) = 1056 |
Mr = 250.25 | Dx = 1.361 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1720 (14) Å | Cell parameters from 1664 reflections |
b = 13.3180 (15) Å | θ = 2.3–22.3° |
c = 17.116 (2) Å | µ = 0.10 mm−1 |
β = 118.300 (2)° | T = 298 K |
V = 2443.0 (5) Å3 | Block, yellow |
Z = 8 | 0.48 × 0.45 × 0.17 mm |
Bruker SMART APEX CCD area-detector diffractometer | 4298 independent reflections |
Radiation source: fine-focus sealed tube | 1943 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
φ and ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.952, Tmax = 0.983 | k = −14→15 |
11604 measured reflections | l = −20→19 |
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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.237 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.1244P)2] where P = (Fo2 + 2Fc2)/3 |
4298 reflections | (Δ/σ)max = 0.001 |
338 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C12H14N2O4 | V = 2443.0 (5) Å3 |
Mr = 250.25 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.1720 (14) Å | µ = 0.10 mm−1 |
b = 13.3180 (15) Å | T = 298 K |
c = 17.116 (2) Å | 0.48 × 0.45 × 0.17 mm |
β = 118.300 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 4298 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1943 reflections with I > 2σ(I) |
Tmin = 0.952, Tmax = 0.983 | Rint = 0.069 |
11604 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.237 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.30 e Å−3 |
4298 reflections | Δρmin = −0.23 e Å−3 |
338 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) | |
N1 | 0.0677 (3) | 0.8975 (2) | 0.4632 (2) | 0.0478 (9) | |
H1 | 0.0351 | 0.9555 | 0.4437 | 0.057* | |
N2 | 0.0574 (3) | 0.7467 (2) | 0.5219 (2) | 0.0479 (8) | |
H2 | 0.0468 | 0.7135 | 0.5609 | 0.057* | |
N3 | 0.8736 (3) | 0.6124 (2) | 0.7072 (2) | 0.0499 (9) | |
H3 | 0.8988 | 0.5511 | 0.7182 | 0.060* | |
N4 | 0.8981 (3) | 0.7698 (2) | 0.6635 (2) | 0.0497 (8) | |
H4 | 0.9196 | 0.8075 | 0.6321 | 0.060* | |
O1 | −0.0199 (2) | 0.88634 (18) | 0.55364 (19) | 0.0574 (8) | |
O2 | 0.3239 (6) | 0.8613 (5) | 0.5879 (5) | 0.086 (2) | 0.625 (6) |
C4' | 0.3192 (18) | 0.9228 (13) | 0.5941 (13) | 0.086 (2) | 0.375 (6) |
H4' | 0.2672 | 0.9425 | 0.6173 | 0.103* | 0.375 (6) |
O3 | 0.2203 (2) | 0.7669 (2) | 0.32562 (17) | 0.0565 (8) | |
O4 | 0.1728 (3) | 0.6108 (2) | 0.3447 (2) | 0.0686 (9) | |
O5 | 0.9657 (3) | 0.63333 (18) | 0.6200 (2) | 0.0600 (8) | |
O6 | 0.6054 (4) | 0.6411 (3) | 0.5976 (3) | 0.1107 (13) | |
O7 | 0.7327 (3) | 0.7358 (2) | 0.85737 (19) | 0.0690 (9) | |
O8 | 0.7471 (3) | 0.8936 (2) | 0.8223 (2) | 0.0780 (10) | |
C1 | 0.0329 (3) | 0.8474 (3) | 0.5145 (3) | 0.0456 (10) | |
C2 | 0.1585 (3) | 0.8589 (3) | 0.4384 (3) | 0.0429 (10) | |
H2A | 0.1438 | 0.8907 | 0.3826 | 0.052* | |
C3 | 0.2873 (4) | 0.8830 (3) | 0.5074 (3) | 0.0559 (11) | |
C4 | 0.3859 (8) | 0.9166 (7) | 0.4951 (7) | 0.079 (2) | 0.625 (6) |
H4A | 0.3852 | 0.9349 | 0.4424 | 0.094* | 0.625 (6) |
C5 | 0.4870 (15) | 0.9164 (9) | 0.5815 (12) | 0.086 (4) | 0.625 (6) |
H5 | 0.5680 | 0.9359 | 0.5966 | 0.103* | 0.625 (6) |
C6 | 0.448 (2) | 0.8828 (11) | 0.6403 (17) | 0.091 (4) | 0.625 (6) |
H6 | 0.4943 | 0.8764 | 0.7016 | 0.109* | 0.625 (6) |
O2' | 0.3875 (9) | 0.8450 (8) | 0.5162 (7) | 0.079 (2) | 0.375 (6) |
C5' | 0.459 (4) | 0.924 (2) | 0.636 (3) | 0.091 (4) | 0.375 (6) |
H5' | 0.5116 | 0.9619 | 0.6855 | 0.109* | 0.375 (6) |
C6' | 0.492 (3) | 0.8685 (16) | 0.598 (2) | 0.086 (4) | 0.375 (6) |
H6' | 0.5725 | 0.8445 | 0.6184 | 0.103* | 0.375 (6) |
C7 | 0.1783 (3) | 0.6992 (3) | 0.3629 (2) | 0.0461 (9) | |
C8 | 0.1410 (3) | 0.7470 (2) | 0.4236 (2) | 0.0408 (9) | |
C9 | 0.0980 (3) | 0.6952 (3) | 0.4705 (2) | 0.0425 (9) | |
C10 | 0.0877 (4) | 0.5845 (3) | 0.4755 (3) | 0.0621 (12) | |
H10A | 0.0024 | 0.5646 | 0.4395 | 0.093* | |
H10B | 0.1149 | 0.5652 | 0.5359 | 0.093* | |
H10C | 0.1390 | 0.5523 | 0.4542 | 0.093* | |
C11 | 0.2614 (4) | 0.7310 (3) | 0.2650 (3) | 0.0666 (12) | |
H11A | 0.1938 | 0.6969 | 0.2155 | 0.080* | |
H11B | 0.3299 | 0.6842 | 0.2946 | 0.080* | |
C12 | 0.3030 (4) | 0.8203 (4) | 0.2328 (3) | 0.0828 (15) | |
H12A | 0.2344 | 0.8660 | 0.2037 | 0.124* | |
H12B | 0.3312 | 0.7988 | 0.1918 | 0.124* | |
H12C | 0.3700 | 0.8533 | 0.2823 | 0.124* | |
C13 | 0.9139 (3) | 0.6678 (3) | 0.6603 (3) | 0.0473 (10) | |
C14 | 0.7910 (3) | 0.6476 (3) | 0.7409 (3) | 0.0477 (10) | |
H14 | 0.8183 | 0.6161 | 0.7989 | 0.057* | |
C15 | 0.6605 (4) | 0.6159 (3) | 0.6829 (3) | 0.0588 (12) | |
C16 | 0.5810 (5) | 0.5651 (4) | 0.7005 (4) | 0.0925 (17) | |
H16 | 0.5969 | 0.5387 | 0.7552 | 0.111* | |
C17 | 0.4691 (6) | 0.5587 (5) | 0.6215 (6) | 0.113 (2) | |
H17 | 0.3961 | 0.5281 | 0.6141 | 0.136* | |
C18 | 0.4851 (6) | 0.6031 (6) | 0.5604 (6) | 0.126 (3) | |
H18 | 0.4254 | 0.6087 | 0.5011 | 0.151* | |
C19 | 0.7596 (4) | 0.8057 (3) | 0.8129 (3) | 0.0563 (11) | |
C20 | 0.8035 (3) | 0.7603 (3) | 0.7555 (2) | 0.0452 (9) | |
C21 | 0.8509 (3) | 0.8162 (3) | 0.7128 (2) | 0.0444 (9) | |
C22 | 0.8605 (4) | 0.9280 (3) | 0.7135 (3) | 0.0591 (12) | |
H22A | 0.7799 | 0.9562 | 0.6756 | 0.089* | |
H22B | 0.9178 | 0.9474 | 0.6924 | 0.089* | |
H22C | 0.8901 | 0.9524 | 0.7729 | 0.089* | |
C23 | 0.6852 (5) | 0.7708 (4) | 0.9158 (3) | 0.0831 (15) | |
H23A | 0.6148 | 0.8154 | 0.8839 | 0.100* | |
H23B | 0.7496 | 0.8074 | 0.9654 | 0.100* | |
C24 | 0.6464 (5) | 0.6833 (5) | 0.9477 (4) | 0.110 (2) | |
H24A | 0.5780 | 0.6508 | 0.8987 | 0.165* | |
H24B | 0.6206 | 0.7041 | 0.9903 | 0.165* | |
H24C | 0.7150 | 0.6373 | 0.9753 | 0.165* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.047 (2) | 0.0349 (18) | 0.072 (2) | 0.0098 (14) | 0.037 (2) | 0.0113 (15) |
N2 | 0.058 (2) | 0.0331 (19) | 0.065 (2) | 0.0014 (15) | 0.0384 (19) | 0.0075 (14) |
N3 | 0.053 (2) | 0.0363 (18) | 0.074 (2) | 0.0055 (14) | 0.041 (2) | 0.0085 (15) |
N4 | 0.056 (2) | 0.0355 (19) | 0.068 (2) | 0.0017 (15) | 0.038 (2) | 0.0059 (15) |
O1 | 0.0673 (18) | 0.0414 (16) | 0.088 (2) | 0.0067 (13) | 0.0563 (18) | 0.0067 (14) |
O2 | 0.068 (3) | 0.082 (5) | 0.086 (4) | −0.010 (4) | 0.019 (3) | 0.002 (5) |
C4' | 0.068 (3) | 0.082 (5) | 0.086 (4) | −0.010 (4) | 0.019 (3) | 0.002 (5) |
O3 | 0.0712 (19) | 0.0502 (17) | 0.0654 (18) | −0.0097 (13) | 0.0466 (17) | −0.0051 (13) |
O4 | 0.089 (2) | 0.0406 (18) | 0.097 (2) | −0.0088 (15) | 0.061 (2) | −0.0133 (15) |
O5 | 0.0728 (19) | 0.0429 (17) | 0.091 (2) | 0.0006 (14) | 0.0604 (19) | 0.0001 (14) |
O6 | 0.077 (3) | 0.116 (3) | 0.105 (3) | −0.018 (2) | 0.015 (3) | 0.006 (2) |
O7 | 0.083 (2) | 0.070 (2) | 0.076 (2) | −0.0077 (16) | 0.055 (2) | −0.0078 (16) |
O8 | 0.100 (3) | 0.052 (2) | 0.105 (3) | −0.0020 (17) | 0.066 (2) | −0.0134 (17) |
C1 | 0.041 (2) | 0.041 (2) | 0.064 (3) | 0.0000 (17) | 0.032 (2) | 0.0031 (19) |
C2 | 0.044 (2) | 0.037 (2) | 0.055 (2) | −0.0022 (17) | 0.030 (2) | 0.0033 (17) |
C3 | 0.049 (3) | 0.041 (2) | 0.074 (3) | −0.001 (2) | 0.027 (3) | −0.004 (2) |
C4 | 0.058 (3) | 0.084 (6) | 0.090 (5) | −0.003 (5) | 0.031 (4) | −0.011 (5) |
C5 | 0.052 (4) | 0.090 (11) | 0.100 (9) | −0.006 (8) | 0.024 (6) | −0.015 (9) |
C6 | 0.068 (6) | 0.081 (14) | 0.095 (6) | −0.007 (10) | 0.016 (5) | −0.005 (11) |
O2' | 0.058 (3) | 0.084 (6) | 0.090 (5) | −0.003 (5) | 0.031 (4) | −0.011 (5) |
C5' | 0.068 (6) | 0.081 (14) | 0.095 (6) | −0.007 (10) | 0.016 (5) | −0.005 (11) |
C6' | 0.052 (4) | 0.090 (11) | 0.100 (9) | −0.006 (8) | 0.024 (6) | −0.015 (9) |
C7 | 0.043 (2) | 0.045 (3) | 0.053 (2) | −0.0040 (18) | 0.025 (2) | −0.0023 (19) |
C8 | 0.040 (2) | 0.033 (2) | 0.053 (2) | −0.0022 (16) | 0.025 (2) | −0.0002 (16) |
C9 | 0.041 (2) | 0.037 (2) | 0.057 (2) | −0.0012 (16) | 0.029 (2) | −0.0004 (17) |
C10 | 0.079 (3) | 0.035 (2) | 0.091 (3) | −0.009 (2) | 0.055 (3) | −0.005 (2) |
C11 | 0.075 (3) | 0.070 (3) | 0.071 (3) | −0.005 (2) | 0.048 (3) | −0.004 (2) |
C12 | 0.086 (4) | 0.094 (4) | 0.088 (4) | −0.023 (3) | 0.057 (3) | −0.005 (3) |
C13 | 0.044 (2) | 0.039 (2) | 0.064 (3) | 0.0000 (17) | 0.029 (2) | 0.0050 (18) |
C14 | 0.049 (2) | 0.044 (2) | 0.059 (3) | 0.0016 (18) | 0.033 (2) | 0.0051 (18) |
C15 | 0.054 (3) | 0.049 (3) | 0.081 (4) | −0.005 (2) | 0.038 (3) | −0.007 (2) |
C16 | 0.077 (4) | 0.106 (5) | 0.107 (5) | −0.027 (3) | 0.054 (4) | −0.013 (3) |
C17 | 0.068 (4) | 0.110 (6) | 0.161 (7) | −0.021 (4) | 0.054 (5) | −0.043 (5) |
C18 | 0.069 (5) | 0.127 (6) | 0.123 (7) | −0.007 (4) | −0.002 (5) | −0.019 (5) |
C19 | 0.046 (3) | 0.059 (3) | 0.066 (3) | −0.005 (2) | 0.028 (2) | −0.003 (2) |
C20 | 0.038 (2) | 0.041 (2) | 0.057 (2) | 0.0002 (17) | 0.022 (2) | −0.0021 (18) |
C21 | 0.038 (2) | 0.037 (2) | 0.058 (3) | −0.0007 (16) | 0.022 (2) | −0.0011 (17) |
C22 | 0.063 (3) | 0.039 (2) | 0.080 (3) | −0.0017 (19) | 0.037 (3) | 0.000 (2) |
C23 | 0.103 (4) | 0.090 (4) | 0.082 (3) | −0.009 (3) | 0.065 (3) | −0.013 (3) |
C24 | 0.122 (5) | 0.140 (6) | 0.106 (4) | −0.030 (4) | 0.084 (4) | −0.017 (4) |
N1—C1 | 1.322 (4) | O2'—C6' | 1.41 (3) |
N1—C2 | 1.454 (4) | C5'—C6' | 1.17 (6) |
N1—H1 | 0.8600 | C5'—H5' | 0.9300 |
N2—C1 | 1.365 (4) | C6'—H6' | 0.9300 |
N2—C9 | 1.379 (4) | C7—C8 | 1.462 (5) |
N2—H2 | 0.8600 | C8—C9 | 1.339 (5) |
N3—C13 | 1.343 (5) | C9—C10 | 1.485 (5) |
N3—C14 | 1.454 (4) | C10—H10A | 0.9600 |
N3—H3 | 0.8600 | C10—H10B | 0.9600 |
N4—C21 | 1.373 (4) | C10—H10C | 0.9600 |
N4—C13 | 1.377 (4) | C11—C12 | 1.496 (6) |
N4—H4 | 0.8600 | C11—H11A | 0.9700 |
O1—C1 | 1.241 (4) | C11—H11B | 0.9700 |
O2—C3 | 1.263 (8) | C12—H12A | 0.9600 |
O2—C6 | 1.37 (2) | C12—H12B | 0.9600 |
C4'—C3 | 1.44 (2) | C12—H12C | 0.9600 |
C4'—C5' | 1.50 (5) | C14—C15 | 1.480 (5) |
C4'—H4' | 0.9300 | C14—C20 | 1.518 (5) |
O3—C7 | 1.338 (4) | C14—H14 | 0.9800 |
O3—C11 | 1.430 (4) | C15—C16 | 1.327 (6) |
O4—C7 | 1.211 (4) | C16—C17 | 1.395 (8) |
O5—C13 | 1.224 (4) | C16—H16 | 0.9300 |
O6—C15 | 1.330 (6) | C17—C18 | 1.294 (9) |
O6—C18 | 1.387 (7) | C17—H17 | 0.9300 |
O7—C19 | 1.337 (5) | C18—H18 | 0.9300 |
O7—C23 | 1.449 (5) | C19—C20 | 1.455 (5) |
O8—C19 | 1.201 (4) | C20—C21 | 1.349 (5) |
C2—C3 | 1.484 (5) | C21—C22 | 1.494 (5) |
C2—C8 | 1.509 (5) | C22—H22A | 0.9600 |
C2—H2A | 0.9800 | C22—H22B | 0.9600 |
C3—O2' | 1.262 (10) | C22—H22C | 0.9600 |
C3—C4 | 1.387 (10) | C23—C24 | 1.458 (7) |
C4—C5 | 1.405 (18) | C23—H23A | 0.9700 |
C4—H4A | 0.9300 | C23—H23B | 0.9700 |
C5—C6 | 1.38 (3) | C24—H24A | 0.9600 |
C5—H5 | 0.9300 | C24—H24B | 0.9600 |
C6—H6 | 0.9300 | C24—H24C | 0.9600 |
C1—N1—C2 | 122.9 (3) | H10A—C10—H10B | 109.5 |
C1—N1—H1 | 118.6 | C9—C10—H10C | 109.5 |
C2—N1—H1 | 118.6 | H10A—C10—H10C | 109.5 |
C1—N2—C9 | 123.9 (3) | H10B—C10—H10C | 109.5 |
C1—N2—H2 | 118.0 | O3—C11—C12 | 107.3 (4) |
C9—N2—H2 | 118.0 | O3—C11—H11A | 110.3 |
C13—N3—C14 | 125.2 (3) | C12—C11—H11A | 110.3 |
C13—N3—H3 | 117.4 | O3—C11—H11B | 110.3 |
C14—N3—H3 | 117.4 | C12—C11—H11B | 110.3 |
C21—N4—C13 | 125.1 (3) | H11A—C11—H11B | 108.5 |
C21—N4—H4 | 117.5 | C11—C12—H12A | 109.5 |
C13—N4—H4 | 117.5 | C11—C12—H12B | 109.5 |
C3—O2—C6 | 112.1 (12) | H12A—C12—H12B | 109.5 |
C3—C4'—C5' | 101 (2) | C11—C12—H12C | 109.5 |
C3—C4'—H4' | 129.5 | H12A—C12—H12C | 109.5 |
C5'—C4'—H4' | 129.5 | H12B—C12—H12C | 109.5 |
C7—O3—C11 | 117.6 (3) | O5—C13—N3 | 124.2 (4) |
C15—O6—C18 | 106.5 (5) | O5—C13—N4 | 120.8 (3) |
C19—O7—C23 | 117.0 (4) | N3—C13—N4 | 115.0 (4) |
O1—C1—N1 | 123.9 (4) | N3—C14—C15 | 111.5 (3) |
O1—C1—N2 | 120.4 (3) | N3—C14—C20 | 110.5 (3) |
N1—C1—N2 | 115.6 (3) | C15—C14—C20 | 112.6 (3) |
N1—C2—C3 | 110.7 (3) | N3—C14—H14 | 107.3 |
N1—C2—C8 | 109.4 (3) | C15—C14—H14 | 107.3 |
C3—C2—C8 | 111.0 (3) | C20—C14—H14 | 107.3 |
N1—C2—H2A | 108.5 | C16—C15—O6 | 109.7 (5) |
C3—C2—H2A | 108.5 | C16—C15—C14 | 131.2 (5) |
C8—C2—H2A | 108.5 | O6—C15—C14 | 119.1 (4) |
O2'—C3—O2 | 87.6 (7) | C15—C16—C17 | 107.0 (6) |
O2'—C3—C4 | 44.8 (5) | C15—C16—H16 | 126.5 |
O2—C3—C4 | 110.9 (6) | C17—C16—H16 | 126.5 |
O2'—C3—C4' | 104.6 (10) | C18—C17—C16 | 107.7 (6) |
O2—C3—C4' | 35.0 (6) | C18—C17—H17 | 126.2 |
C4—C3—C4' | 101.9 (9) | C16—C17—H17 | 126.2 |
O2'—C3—C2 | 127.2 (6) | C17—C18—O6 | 109.1 (7) |
O2—C3—C2 | 120.8 (5) | C17—C18—H18 | 125.4 |
C4—C3—C2 | 127.8 (6) | O6—C18—H18 | 125.4 |
C4'—C3—C2 | 124.4 (9) | O8—C19—O7 | 121.5 (4) |
C3—C4—C5 | 103.2 (10) | O8—C19—C20 | 127.3 (4) |
C3—C4—H4A | 128.4 | O7—C19—C20 | 111.3 (4) |
C5—C4—H4A | 128.4 | C21—C20—C19 | 121.7 (4) |
C6—C5—C4 | 109.5 (15) | C21—C20—C14 | 119.5 (3) |
C6—C5—H5 | 125.2 | C19—C20—C14 | 118.8 (3) |
C4—C5—H5 | 125.2 | C20—C21—N4 | 119.7 (3) |
O2—C6—C5 | 104.1 (18) | C20—C21—C22 | 126.7 (3) |
O2—C6—H6 | 127.9 | N4—C21—C22 | 113.5 (3) |
C5—C6—H6 | 127.9 | C21—C22—H22A | 109.5 |
C3—O2'—C6' | 113.1 (15) | C21—C22—H22B | 109.5 |
C6'—C5'—C4' | 110 (3) | H22A—C22—H22B | 109.5 |
C6'—C5'—H5' | 125.2 | C21—C22—H22C | 109.5 |
C4'—C5'—H5' | 125.2 | H22A—C22—H22C | 109.5 |
C5'—C6'—O2' | 108 (3) | H22B—C22—H22C | 109.5 |
C5'—C6'—H6' | 125.9 | O7—C23—C24 | 107.9 (4) |
O2'—C6'—H6' | 125.9 | O7—C23—H23A | 110.1 |
O4—C7—O3 | 121.3 (3) | C24—C23—H23A | 110.1 |
O4—C7—C8 | 127.4 (3) | O7—C23—H23B | 110.1 |
O3—C7—C8 | 111.2 (3) | C24—C23—H23B | 110.1 |
C9—C8—C7 | 122.9 (3) | H23A—C23—H23B | 108.4 |
C9—C8—C2 | 118.2 (3) | C23—C24—H24A | 109.5 |
C7—C8—C2 | 118.9 (3) | C23—C24—H24B | 109.5 |
C8—C9—N2 | 119.1 (3) | H24A—C24—H24B | 109.5 |
C8—C9—C10 | 127.9 (3) | C23—C24—H24C | 109.5 |
N2—C9—C10 | 113.0 (3) | H24A—C24—H24C | 109.5 |
C9—C10—H10A | 109.5 | H24B—C24—H24C | 109.5 |
C9—C10—H10B | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.12 | 2.924 (4) | 156 |
N2—H2···O5ii | 0.86 | 2.02 | 2.851 (4) | 162 |
N3—H3···O4iii | 0.86 | 2.38 | 3.077 (4) | 138 |
N4—H4···O1iv | 0.86 | 2.10 | 2.952 (4) | 174 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C12H14N2O4 |
Mr | 250.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 12.1720 (14), 13.3180 (15), 17.116 (2) |
β (°) | 118.300 (2) |
V (Å3) | 2443.0 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.48 × 0.45 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.952, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11604, 4298, 1943 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.237, 0.94 |
No. of reflections | 4298 |
No. of parameters | 338 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.23 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.12 | 2.924 (4) | 156.0 |
N2—H2···O5ii | 0.86 | 2.02 | 2.851 (4) | 161.6 |
N3—H3···O4iii | 0.86 | 2.38 | 3.077 (4) | 138.0 |
N4—H4···O1iv | 0.86 | 2.10 | 2.952 (4) | 174.3 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z. |
Acknowledgements
The authors acknowledge financial support by the Foundation of Binzhou University (grant No. BZXYQNLG2005015).
References
Biginelli, P. (1893). Gazz. Chim. Ital. 23, 360–413. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Nizam Mohideen, M., Rasheeth, A., Huq, C. A. M. A. & Nizar, S. S. (2008). Acta Cryst. E64, o1752. Web of Science CSD CrossRef IUCr Journals Google Scholar
Qing-Fang, C., Xu, X.-Y., Bao, J.-Y. & Zhang, C.-F. (2007). Acta Cryst. E63, o2391–o2392. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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.
Biginelli reaction is a well known multicomponent reaction involving a one-pot cyclocondensation of an aldehyde, β-ketoester and urea/thiourea. It is the most important procedure in the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones (Biginelli, 1893). Herewith we report the crystal structure of the title compound, (I), obtained by the three-component reaction of furfuraldehyde, acetoacetate and urea.
In (I) (Fig. 1), the dihydropyrimidinone rings adopt flattened boat conformation. The asymmetric unit contains two independent molecules. In one independent molecule, the furanyl fragment is rotationally disordered in a ratio 0.625 (6):0.375 (6). The bond lengths an angles are normal and comparable to the values observed in similar compounds (Nizam Mohideen et al., 2008; Qing-Fang et al., 2007) The dihedral angles between the furan rings (C3—C6/O2, C15—C18/O6) and the mean planes of the dihydropyrimidinone rings (N1/C1/N2/C9/C8, N3/C13/N4/C21/C20) unit in two independent molecules are 88.79 (4) ° and 86.73 (2)°, respectively, indicating that the furan rings and the dihydropyrimidinone rings are nearly perpendicular.
In the crystal structure, intermolecular N—H···Opyrimidinone hydrogen bonds (Table 1) link the molecules into centrosymmetric tetramers. Tetramers are further associated into ribbons extended in direction [010] via the weak intermolecular N—H···Ocarboxyl hydrogen bonds (Table 1).