organic compounds
rac-Ethyl 2-hydroxy-2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-3,4,5,6,7,8-hexahydro-2H-chromene-3-carboxylate
aBaku State University, Baku, Z. Khalilov St 23, AZ-1148, Azerbaijan, and bVladimir State University, 600000 Vladimir, Gor'ky St 87, Russian Federation
*Correspondence e-mail: orglab@mail.ru
The title molecule, C21H25NO7, has four stereogenic centres and crystallized as a racemate. It consists of enantiomeric pairs with the rac-(1R*,2S*,3R*). The cyclohexenone ring adopts an the dimethyl-substituted C atom lies 0.640 (1) Å out of the mean plane formed by the rest of the ring atoms (r.m.s. deviation = 0.016 Å). The oxacyclohexene ring adopts a half-chair conformation, the hydroxy- and carboxyl-substituted C atoms lying −0.336 (1) and 0.419 (1) Å, respectively, out of the mean plane formed by the rest of the ring atoms (r.m.s. deviation = 0.002 Å). In the crystal, O—H⋯O hydrogen bonds link the molecules into a chain along the c-axis direction.
Related literature
For general background to 2H-chromenes and their derivatives, see: Cai (2008); Valenti et al. (1993); Hyana & Saimoto (1987); Tang et al. (2007). For their anticancer activity, see: Afantitis et al. (2006); Cai (2007). For puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus; 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.
Supporting information
https://doi.org/10.1107/S1600536812050581/aa2078sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050581/aa2078Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050581/aa2078Isup3.cml
Dimedone (5 mmol), 4-nitrobenzaldehyde (5 mmol) and acetoacetic ether (5 mmol) were dissolved in ethanol (15 ml). Then allylamine (0.4 ml) was added and mixture was stirred at 300 K for 3 h. Obtained yellow crystals were filtered and washed with ethanol. The crystals were dissolved in ethanol (20 ml) and recrystallized to yield yellow crystals of the title compound suitable for X-ray analysis.
Hydrogen atom of the OH group was found in difference-Fourier maps and included in the
with isotropic displacement parameter. The other hydrogen atoms were placed in calculated positions and refined in the riding mode with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C)].2H-chromenes and their derivatives possess various biological and pharmacological properties such as anti-viral, anti-fungal, anti-inflammatory, antidiabetic, cardionthonic, anti-anaphylactic and anti-cancer activity (Cai, 2008; Valenti et al., 1993; Hyana & Saimoto, 1987; Tang et al., 2007). 2H-chromenes are a new series of apoptosis inducers, which exhibit potent anticancer activity (Afantitis et al., 2006; Cai, 2007;). Considering the importance of 2H-chromene-3-carboxylate derivatives, a single-crystal X-ray diffraction study on the title compound was carried out and analyzed.
A simple synthesis of new and biologically active ethyl 2-hydroxy-2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-3,4,5,6,7,8-hexahydro-2H- chromene-3-carboxylate (Fig. 1) was carried out using cyclocondensation reaction of 4-nitrobenzaldehyde, acetoacetic ether and dimedone with allylamine as catalizator at room temperature. The title molecule is chiral with four stereogenic centres. The crystal is a racemate and consists of enantiomeric pairs with the
rac-(1R*, 2S*, 3R*). The cyclohexenone ring adopt a C7 lies 0.640 (1) Å out of the plane formed by the rest of the ring atoms (r.m.s. deviation = 0.016 Å). The oxacyclohexene ring adopt a half-chair conformation, C1 and C2 lie -0.336 (1) and 0.419 (1) Å respectively out of the plane formed by the rest of the ring (r.m.s. deviation = 0.002 Å). The 4-nitrophenyl ring is in a pseudo-equatorial position. The torsion angle between the ethoxycarbonyl group and the 4-nirtophenyl substituent C11–C2–C3–C14 is -65.16 (13) ° that indicates the pseudo-axial location of hydrogen atoms at C2 and C3. Intermolecular O—H···O hydrogen bonds link molecules into a chain along the c axis (Table 1, Fig. 2).For general background to 2H-chromenes and their derivatives, see: Cai (2008); Valenti et al. (1993); Hyana & Saimoto (1987); Tang et al. (2007). For their anticancer activity, see: Afantitis et al. (2006); Cai (2007). For puckering parameters, see: Cremer & Pople (1975).
Data collection: APEX2 (Bruker, 2005); cell
SAINT-Plus (Bruker, 2005); data reduction: SAINT-Plus (Bruker, 2005); 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).C21H25NO7 | F(000) = 856 |
Mr = 403.42 | Dx = 1.321 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6760 reflections |
a = 10.4163 (8) Å | θ = 2.7–28.5° |
b = 24.2608 (18) Å | µ = 0.10 mm−1 |
c = 8.0796 (6) Å | T = 296 K |
β = 96.437 (2)° | Prism, yellow |
V = 2028.9 (3) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 5078 independent reflections |
Radiation source: fine-focus sealed tube | 4084 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 28.4°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −13→13 |
Tmin = 0.971, Tmax = 0.980 | k = −32→32 |
23423 measured reflections | l = −10→10 |
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)] = 0.044 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0521P)2 + 0.7463P] where P = (Fo2 + 2Fc2)/3 |
5078 reflections | (Δ/σ)max = 0.001 |
266 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C21H25NO7 | V = 2028.9 (3) Å3 |
Mr = 403.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.4163 (8) Å | µ = 0.10 mm−1 |
b = 24.2608 (18) Å | T = 296 K |
c = 8.0796 (6) Å | 0.30 × 0.20 × 0.20 mm |
β = 96.437 (2)° |
Bruker APEXII CCD diffractometer | 5078 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 4084 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.980 | Rint = 0.022 |
23423 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.30 e Å−3 |
5078 reflections | Δρmin = −0.20 e Å−3 |
266 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 > 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 | ||
O1 | 0.06693 (9) | 0.68270 (4) | 0.29152 (11) | 0.0360 (2) | |
O2 | −0.04636 (10) | 0.74080 (4) | 0.10075 (13) | 0.0383 (2) | |
H2 | −0.080 (2) | 0.7620 (9) | 0.162 (3) | 0.061 (6)* | |
O3 | −0.17047 (10) | 0.67735 (4) | −0.21204 (13) | 0.0427 (3) | |
O4 | −0.23488 (9) | 0.60735 (4) | −0.06145 (12) | 0.0366 (2) | |
O5 | 0.23965 (18) | 0.44094 (6) | −0.4474 (2) | 0.0829 (5) | |
O6 | 0.16430 (16) | 0.49162 (6) | −0.65423 (17) | 0.0721 (4) | |
O7 | 0.35300 (11) | 0.66576 (5) | −0.11760 (13) | 0.0508 (3) | |
N1 | 0.18908 (15) | 0.48317 (6) | −0.5053 (2) | 0.0522 (4) | |
C1 | −0.04561 (12) | 0.68823 (6) | 0.16883 (16) | 0.0314 (3) | |
C2 | −0.03255 (12) | 0.64615 (5) | 0.03021 (15) | 0.0297 (3) | |
H2A | −0.0244 | 0.6095 | 0.0812 | 0.036* | |
C3 | 0.08949 (12) | 0.65704 (5) | −0.05552 (16) | 0.0303 (3) | |
H3A | 0.0758 | 0.6908 | −0.1218 | 0.036* | |
C4 | 0.20193 (13) | 0.66649 (6) | 0.07676 (16) | 0.0322 (3) | |
C5 | 0.33285 (14) | 0.66857 (6) | 0.02822 (18) | 0.0370 (3) | |
C6 | 0.44363 (14) | 0.67805 (8) | 0.1622 (2) | 0.0467 (4) | |
H6A | 0.4666 | 0.7168 | 0.1616 | 0.056* | |
H6B | 0.5176 | 0.6573 | 0.1335 | 0.056* | |
C7 | 0.41940 (14) | 0.66238 (7) | 0.33864 (19) | 0.0411 (3) | |
C8 | 0.29096 (13) | 0.68842 (7) | 0.37109 (18) | 0.0393 (3) | |
H8A | 0.2660 | 0.6740 | 0.4748 | 0.047* | |
H8B | 0.3028 | 0.7279 | 0.3842 | 0.047* | |
C9 | 0.18422 (12) | 0.67797 (5) | 0.23553 (17) | 0.0323 (3) | |
C10 | −0.15932 (14) | 0.67843 (7) | 0.26566 (19) | 0.0432 (3) | |
H10A | −0.1609 | 0.7063 | 0.3498 | 0.065* | |
H10B | −0.1514 | 0.6428 | 0.3174 | 0.065* | |
H10C | −0.2379 | 0.6800 | 0.1914 | 0.065* | |
C11 | −0.15205 (12) | 0.64616 (5) | −0.09602 (16) | 0.0310 (3) | |
C12 | −0.35486 (14) | 0.60395 (7) | −0.17297 (19) | 0.0407 (3) | |
H12A | −0.3363 | 0.6005 | −0.2875 | 0.049* | |
H12B | −0.4062 | 0.6369 | −0.1634 | 0.049* | |
C13 | −0.42646 (19) | 0.55435 (8) | −0.1231 (3) | 0.0638 (5) | |
H13A | −0.5062 | 0.5509 | −0.1944 | 0.096* | |
H13B | −0.4443 | 0.5583 | −0.0097 | 0.096* | |
H13C | −0.3748 | 0.5220 | −0.1333 | 0.096* | |
C14 | 0.11142 (13) | 0.60989 (6) | −0.17235 (16) | 0.0325 (3) | |
C15 | 0.08635 (14) | 0.61724 (6) | −0.34299 (17) | 0.0371 (3) | |
H15A | 0.0540 | 0.6508 | −0.3847 | 0.044* | |
C16 | 0.10879 (15) | 0.57534 (6) | −0.45185 (18) | 0.0410 (3) | |
H16A | 0.0915 | 0.5804 | −0.5663 | 0.049* | |
C17 | 0.15694 (14) | 0.52615 (6) | −0.38837 (19) | 0.0396 (3) | |
C18 | 0.17904 (16) | 0.51659 (6) | −0.2196 (2) | 0.0456 (4) | |
H18A | 0.2094 | 0.4826 | −0.1788 | 0.055* | |
C19 | 0.15505 (16) | 0.55868 (6) | −0.11237 (18) | 0.0428 (3) | |
H19A | 0.1683 | 0.5527 | 0.0020 | 0.051* | |
C20 | 0.41427 (19) | 0.59983 (8) | 0.3586 (3) | 0.0623 (5) | |
H20A | 0.4956 | 0.5841 | 0.3380 | 0.093* | |
H20B | 0.3467 | 0.5850 | 0.2806 | 0.093* | |
H20C | 0.3973 | 0.5910 | 0.4699 | 0.093* | |
C21 | 0.52760 (16) | 0.68578 (9) | 0.4625 (2) | 0.0565 (5) | |
H21A | 0.6084 | 0.6694 | 0.4427 | 0.085* | |
H21B | 0.5101 | 0.6776 | 0.5740 | 0.085* | |
H21C | 0.5322 | 0.7250 | 0.4485 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0287 (5) | 0.0509 (6) | 0.0282 (4) | 0.0038 (4) | 0.0028 (4) | −0.0004 (4) |
O2 | 0.0428 (6) | 0.0338 (5) | 0.0386 (5) | 0.0051 (4) | 0.0056 (4) | −0.0010 (4) |
O3 | 0.0407 (6) | 0.0451 (6) | 0.0406 (5) | −0.0048 (4) | −0.0030 (4) | 0.0116 (4) |
O4 | 0.0338 (5) | 0.0386 (5) | 0.0367 (5) | −0.0063 (4) | −0.0001 (4) | 0.0030 (4) |
O5 | 0.1139 (14) | 0.0500 (8) | 0.0884 (11) | 0.0253 (8) | 0.0266 (10) | −0.0098 (7) |
O6 | 0.0927 (11) | 0.0727 (9) | 0.0532 (8) | 0.0037 (8) | 0.0182 (7) | −0.0222 (7) |
O7 | 0.0390 (6) | 0.0750 (8) | 0.0403 (6) | 0.0008 (5) | 0.0130 (5) | −0.0018 (5) |
N1 | 0.0546 (8) | 0.0424 (8) | 0.0626 (9) | −0.0018 (6) | 0.0190 (7) | −0.0137 (7) |
C1 | 0.0268 (6) | 0.0373 (7) | 0.0303 (6) | 0.0010 (5) | 0.0037 (5) | 0.0006 (5) |
C2 | 0.0287 (6) | 0.0310 (6) | 0.0296 (6) | 0.0016 (5) | 0.0035 (5) | 0.0019 (5) |
C3 | 0.0291 (6) | 0.0326 (6) | 0.0293 (6) | 0.0035 (5) | 0.0043 (5) | 0.0014 (5) |
C4 | 0.0277 (6) | 0.0348 (7) | 0.0341 (6) | 0.0019 (5) | 0.0036 (5) | 0.0006 (5) |
C5 | 0.0322 (7) | 0.0394 (7) | 0.0399 (7) | 0.0011 (5) | 0.0065 (6) | 0.0009 (6) |
C6 | 0.0292 (7) | 0.0652 (10) | 0.0461 (8) | −0.0052 (7) | 0.0053 (6) | −0.0018 (7) |
C7 | 0.0297 (7) | 0.0498 (9) | 0.0429 (8) | 0.0030 (6) | 0.0002 (6) | 0.0019 (6) |
C8 | 0.0324 (7) | 0.0495 (8) | 0.0349 (7) | 0.0022 (6) | −0.0005 (5) | −0.0021 (6) |
C9 | 0.0277 (6) | 0.0341 (7) | 0.0348 (7) | 0.0029 (5) | 0.0027 (5) | 0.0024 (5) |
C10 | 0.0341 (7) | 0.0583 (9) | 0.0389 (8) | −0.0044 (6) | 0.0111 (6) | −0.0066 (7) |
C11 | 0.0301 (6) | 0.0311 (6) | 0.0322 (6) | 0.0009 (5) | 0.0050 (5) | −0.0018 (5) |
C12 | 0.0315 (7) | 0.0476 (8) | 0.0418 (7) | −0.0025 (6) | −0.0008 (6) | −0.0028 (6) |
C13 | 0.0486 (10) | 0.0582 (11) | 0.0821 (13) | −0.0178 (8) | −0.0033 (9) | 0.0004 (10) |
C14 | 0.0294 (6) | 0.0362 (7) | 0.0321 (6) | 0.0027 (5) | 0.0047 (5) | −0.0005 (5) |
C15 | 0.0412 (7) | 0.0371 (7) | 0.0336 (7) | 0.0074 (6) | 0.0073 (6) | 0.0021 (5) |
C16 | 0.0461 (8) | 0.0454 (8) | 0.0324 (7) | 0.0014 (6) | 0.0087 (6) | −0.0019 (6) |
C17 | 0.0379 (7) | 0.0371 (7) | 0.0453 (8) | −0.0003 (6) | 0.0112 (6) | −0.0077 (6) |
C18 | 0.0509 (9) | 0.0348 (7) | 0.0509 (9) | 0.0091 (6) | 0.0041 (7) | 0.0015 (6) |
C19 | 0.0517 (9) | 0.0407 (8) | 0.0349 (7) | 0.0074 (7) | 0.0001 (6) | 0.0028 (6) |
C20 | 0.0519 (10) | 0.0541 (11) | 0.0790 (13) | 0.0110 (8) | −0.0003 (9) | 0.0108 (9) |
C21 | 0.0344 (8) | 0.0817 (13) | 0.0508 (9) | 0.0015 (8) | −0.0066 (7) | −0.0023 (9) |
O1—C9 | 1.3544 (16) | C8—C9 | 1.4924 (18) |
O1—C1 | 1.4541 (15) | C8—H8A | 0.9700 |
O2—C1 | 1.3885 (17) | C8—H8B | 0.9700 |
O2—H2 | 0.82 (2) | C10—H10A | 0.9600 |
O3—C11 | 1.2032 (16) | C10—H10B | 0.9600 |
O4—C11 | 1.3278 (16) | C10—H10C | 0.9600 |
O4—C12 | 1.4588 (17) | C12—C13 | 1.494 (2) |
O5—N1 | 1.221 (2) | C12—H12A | 0.9700 |
O6—N1 | 1.219 (2) | C12—H12B | 0.9700 |
O7—C5 | 1.2216 (17) | C13—H13A | 0.9600 |
N1—C17 | 1.4706 (19) | C13—H13B | 0.9600 |
C1—C10 | 1.5096 (19) | C13—H13C | 0.9600 |
C1—C2 | 1.5328 (18) | C14—C15 | 1.3857 (19) |
C2—C11 | 1.5182 (18) | C14—C19 | 1.391 (2) |
C2—C3 | 1.5373 (18) | C15—C16 | 1.381 (2) |
C2—H2A | 0.9800 | C15—H15A | 0.9300 |
C3—C4 | 1.5119 (18) | C16—C17 | 1.372 (2) |
C3—C14 | 1.5166 (18) | C16—H16A | 0.9300 |
C3—H3A | 0.9800 | C17—C18 | 1.377 (2) |
C4—C9 | 1.3454 (19) | C18—C19 | 1.380 (2) |
C4—C5 | 1.4615 (19) | C18—H18A | 0.9300 |
C5—C6 | 1.509 (2) | C19—H19A | 0.9300 |
C6—C7 | 1.524 (2) | C20—H20A | 0.9600 |
C6—H6A | 0.9700 | C20—H20B | 0.9600 |
C6—H6B | 0.9700 | C20—H20C | 0.9600 |
C7—C20 | 1.528 (2) | C21—H21A | 0.9600 |
C7—C8 | 1.529 (2) | C21—H21B | 0.9600 |
C7—C21 | 1.530 (2) | C21—H21C | 0.9600 |
C9—O1—C1 | 117.94 (10) | C1—C10—H10A | 109.5 |
C1—O2—H2 | 108.7 (15) | C1—C10—H10B | 109.5 |
C11—O4—C12 | 116.24 (11) | H10A—C10—H10B | 109.5 |
O6—N1—O5 | 123.61 (15) | C1—C10—H10C | 109.5 |
O6—N1—C17 | 118.46 (15) | H10A—C10—H10C | 109.5 |
O5—N1—C17 | 117.93 (15) | H10B—C10—H10C | 109.5 |
O2—C1—O1 | 108.85 (11) | O3—C11—O4 | 124.00 (12) |
O2—C1—C10 | 112.34 (12) | O3—C11—C2 | 124.80 (12) |
O1—C1—C10 | 104.57 (11) | O4—C11—C2 | 111.20 (11) |
O2—C1—C2 | 108.62 (10) | O4—C12—C13 | 107.34 (13) |
O1—C1—C2 | 107.81 (10) | O4—C12—H12A | 110.2 |
C10—C1—C2 | 114.38 (11) | C13—C12—H12A | 110.2 |
C11—C2—C1 | 110.94 (10) | O4—C12—H12B | 110.2 |
C11—C2—C3 | 110.76 (10) | C13—C12—H12B | 110.2 |
C1—C2—C3 | 111.12 (11) | H12A—C12—H12B | 108.5 |
C11—C2—H2A | 108.0 | C12—C13—H13A | 109.5 |
C1—C2—H2A | 108.0 | C12—C13—H13B | 109.5 |
C3—C2—H2A | 108.0 | H13A—C13—H13B | 109.5 |
C4—C3—C14 | 113.29 (11) | C12—C13—H13C | 109.5 |
C4—C3—C2 | 108.77 (10) | H13A—C13—H13C | 109.5 |
C14—C3—C2 | 109.91 (11) | H13B—C13—H13C | 109.5 |
C4—C3—H3A | 108.2 | C15—C14—C19 | 118.63 (13) |
C14—C3—H3A | 108.2 | C15—C14—C3 | 119.84 (12) |
C2—C3—H3A | 108.2 | C19—C14—C3 | 121.53 (12) |
C9—C4—C5 | 118.72 (12) | C16—C15—C14 | 120.83 (13) |
C9—C4—C3 | 121.82 (12) | C16—C15—H15A | 119.6 |
C5—C4—C3 | 119.19 (12) | C14—C15—H15A | 119.6 |
O7—C5—C4 | 121.55 (13) | C17—C16—C15 | 118.89 (13) |
O7—C5—C6 | 120.01 (13) | C17—C16—H16A | 120.6 |
C4—C5—C6 | 118.32 (12) | C15—C16—H16A | 120.6 |
C5—C6—C7 | 116.08 (13) | C16—C17—C18 | 122.03 (13) |
C5—C6—H6A | 108.3 | C16—C17—N1 | 118.47 (14) |
C7—C6—H6A | 108.3 | C18—C17—N1 | 119.48 (14) |
C5—C6—H6B | 108.3 | C17—C18—C19 | 118.37 (14) |
C7—C6—H6B | 108.3 | C17—C18—H18A | 120.8 |
H6A—C6—H6B | 107.4 | C19—C18—H18A | 120.8 |
C6—C7—C20 | 111.00 (15) | C18—C19—C14 | 121.16 (14) |
C6—C7—C8 | 107.29 (12) | C18—C19—H19A | 119.4 |
C20—C7—C8 | 110.53 (14) | C14—C19—H19A | 119.4 |
C6—C7—C21 | 109.40 (14) | C7—C20—H20A | 109.5 |
C20—C7—C21 | 109.35 (14) | C7—C20—H20B | 109.5 |
C8—C7—C21 | 109.22 (13) | H20A—C20—H20B | 109.5 |
C9—C8—C7 | 113.47 (12) | C7—C20—H20C | 109.5 |
C9—C8—H8A | 108.9 | H20A—C20—H20C | 109.5 |
C7—C8—H8A | 108.9 | H20B—C20—H20C | 109.5 |
C9—C8—H8B | 108.9 | C7—C21—H21A | 109.5 |
C7—C8—H8B | 108.9 | C7—C21—H21B | 109.5 |
H8A—C8—H8B | 107.7 | H21A—C21—H21B | 109.5 |
C4—C9—O1 | 124.14 (12) | C7—C21—H21C | 109.5 |
C4—C9—C8 | 124.36 (12) | H21A—C21—H21C | 109.5 |
O1—C9—C8 | 111.48 (11) | H21B—C21—H21C | 109.5 |
C9—O1—C1—O2 | −73.27 (14) | C5—C4—C9—C8 | −5.2 (2) |
C9—O1—C1—C10 | 166.48 (12) | C3—C4—C9—C8 | −179.15 (13) |
C9—O1—C1—C2 | 44.38 (15) | C1—O1—C9—C4 | −14.56 (19) |
O2—C1—C2—C11 | −66.83 (13) | C1—O1—C9—C8 | 164.06 (11) |
O1—C1—C2—C11 | 175.37 (10) | C7—C8—C9—C4 | −24.3 (2) |
C10—C1—C2—C11 | 59.55 (15) | C7—C8—C9—O1 | 157.08 (12) |
O2—C1—C2—C3 | 56.85 (13) | C12—O4—C11—O3 | −0.54 (19) |
O1—C1—C2—C3 | −60.94 (13) | C12—O4—C11—C2 | 179.02 (11) |
C10—C1—C2—C3 | −176.77 (11) | C1—C2—C11—O3 | 84.53 (16) |
C11—C2—C3—C4 | 170.27 (11) | C3—C2—C11—O3 | −39.36 (18) |
C1—C2—C3—C4 | 46.48 (14) | C1—C2—C11—O4 | −95.03 (13) |
C11—C2—C3—C14 | −65.16 (13) | C3—C2—C11—O4 | 141.08 (11) |
C1—C2—C3—C14 | 171.05 (10) | C11—O4—C12—C13 | 174.00 (14) |
C14—C3—C4—C9 | −138.81 (13) | C4—C3—C14—C15 | −131.87 (13) |
C2—C3—C4—C9 | −16.27 (17) | C2—C3—C14—C15 | 106.22 (14) |
C14—C3—C4—C5 | 47.28 (17) | C4—C3—C14—C19 | 48.91 (18) |
C2—C3—C4—C5 | 169.83 (12) | C2—C3—C14—C19 | −73.00 (16) |
C9—C4—C5—O7 | −170.20 (14) | C19—C14—C15—C16 | −2.4 (2) |
C3—C4—C5—O7 | 3.9 (2) | C3—C14—C15—C16 | 178.31 (13) |
C9—C4—C5—C6 | 5.9 (2) | C14—C15—C16—C17 | −0.2 (2) |
C3—C4—C5—C6 | 179.98 (13) | C15—C16—C17—C18 | 2.5 (2) |
O7—C5—C6—C7 | −160.47 (15) | C15—C16—C17—N1 | −175.77 (14) |
C4—C5—C6—C7 | 23.4 (2) | O6—N1—C17—C16 | −4.4 (2) |
C5—C6—C7—C20 | 71.49 (18) | O5—N1—C17—C16 | 175.33 (16) |
C5—C6—C7—C8 | −49.37 (19) | O6—N1—C17—C18 | 177.29 (16) |
C5—C6—C7—C21 | −167.74 (15) | O5—N1—C17—C18 | −2.9 (2) |
C6—C7—C8—C9 | 48.98 (17) | C16—C17—C18—C19 | −1.9 (2) |
C20—C7—C8—C9 | −72.17 (17) | N1—C17—C18—C19 | 176.34 (14) |
C21—C7—C8—C9 | 167.47 (14) | C17—C18—C19—C14 | −0.9 (2) |
C5—C4—C9—O1 | 173.22 (13) | C15—C14—C19—C18 | 3.1 (2) |
C3—C4—C9—O1 | −0.7 (2) | C3—C14—C19—C18 | −177.72 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 (2) | 2.08 (2) | 2.8881 (15) | 172 (2) |
Symmetry code: (i) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C21H25NO7 |
Mr | 403.42 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 10.4163 (8), 24.2608 (18), 8.0796 (6) |
β (°) | 96.437 (2) |
V (Å3) | 2028.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.971, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23423, 5078, 4084 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.118, 1.00 |
No. of reflections | 5078 |
No. of parameters | 266 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.20 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 (2) | 2.08 (2) | 2.8881 (15) | 172 (2) |
Symmetry code: (i) x, −y+3/2, z+1/2. |
Acknowledgements
We thank Baku State University and Vladimir State University for supporting this study.
References
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2H-chromenes and their derivatives possess various biological and pharmacological properties such as anti-viral, anti-fungal, anti-inflammatory, antidiabetic, cardionthonic, anti-anaphylactic and anti-cancer activity (Cai, 2008; Valenti et al., 1993; Hyana & Saimoto, 1987; Tang et al., 2007). 2H-chromenes are a new series of apoptosis inducers, which exhibit potent anticancer activity (Afantitis et al., 2006; Cai, 2007;). Considering the importance of 2H-chromene-3-carboxylate derivatives, a single-crystal X-ray diffraction study on the title compound was carried out and analyzed.
A simple synthesis of new and biologically active ethyl 2-hydroxy-2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-3,4,5,6,7,8-hexahydro-2H- chromene-3-carboxylate (Fig. 1) was carried out using cyclocondensation reaction of 4-nitrobenzaldehyde, acetoacetic ether and dimedone with allylamine as catalizator at room temperature. The title molecule is chiral with four stereogenic centres. The crystal is a racemate and consists of enantiomeric pairs with the relative configuration rac-(1R*, 2S*, 3R*). The cyclohexenone ring adopt a envelope conformation, C7 lies 0.640 (1) Å out of the plane formed by the rest of the ring atoms (r.m.s. deviation = 0.016 Å). The oxacyclohexene ring adopt a half-chair conformation, C1 and C2 lie -0.336 (1) and 0.419 (1) Å respectively out of the plane formed by the rest of the ring (r.m.s. deviation = 0.002 Å). The 4-nitrophenyl ring is in a pseudo-equatorial position. The torsion angle between the ethoxycarbonyl group and the 4-nirtophenyl substituent C11–C2–C3–C14 is -65.16 (13) ° that indicates the pseudo-axial location of hydrogen atoms at C2 and C3. Intermolecular O—H···O hydrogen bonds link molecules into a chain along the c axis (Table 1, Fig. 2).