rac-Ethyl 2-hy­droxy-2,7,7-trimethyl-4-(4-nitro­phen­yl)-5-oxo-3,4,5,6,7,8-hexa­hydro-2H-chromene-3-carboxyl­ate

Maharramov, A.M.; Ismiev, A.I.; Rashidov, B.A.; Askerov, R.K.; Potekhin, K.A.

doi:10.1107/S1600536812050581

organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page o99

https://doi.org/10.1107/S1600536812050581

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rac-Ethyl 2-hydroxy-2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-3,4,5,6,7,8-hexahydro-2H-chromene-3-carboxylate

Abel M. Maharramov,^a Arif I. Ismiev,^a Bahruz A. Rashidov,^a ^* Rizvan K. Askerov ^a and Konstantin A. Potekhin ^b

^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

(Received 14 November 2012; accepted 12 December 2012; online 15 December 2012)

The title molecule, C₂₁H₂₅NO₇, has four stereogenic centres and crystallized as a racemate. It consists of enantiomeric pairs with the relative configuration rac-(1R*,2S*,3R*). The cyclohexenone ring adopts an envelope conformation; 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

C₂₁H₂₅NO₇
M_r = 403.42
Monoclinic, P 2₁ /c
a = 10.4163 (8) Å
b = 24.2608 (18) Å
c = 8.0796 (6) Å
β = 96.437 (2)°
V = 2028.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.971, T_max = 0.980
23423 measured reflections
5078 independent reflections
4084 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.118
S = 1.00
5078 reflections
266 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812050581/aa2078sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
	Fig. 2. The hydrogen-bonded (dashed lines) packing in the title compound (a view perpendicular to the bc plane); H-atoms not involved in hydrogen bonding are omitted for clarity.

rac-Ethyl 2-hydroxy-2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-3,4,5,6,7,8-hexahydro- 2H-chromene-3-carboxylate top

Crystal data top

C₂₁H₂₅NO₇	F(000) = 856
M_r = 403.42	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	5078 independent reflections
Radiation source: fine-focus sealed tube	4084 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 28.4°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −13→13
T_min = 0.971, T_max = 0.980	k = −32→32
23423 measured reflections	l = −10→10

Refinement top

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(F_o²) + (0.0521P)² + 0.7463P] where P = (F_o² + 2F_c²)/3
5078 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₁H₂₅NO₇	V = 2028.9 (3) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	5078 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	4084 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.980	R_int = 0.022
23423 measured reflections

Refinement top

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	Δρ_max = 0.30 e Å⁻³
5078 reflections	Δρ_min = −0.20 e Å⁻³
266 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.971, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	23423, 5078, 4084
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.20

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

Afantitis, A., Melagraki, G., Sarimveis, H., Koutentis, P. A., Markopoulosd, J. & Igglessi-Markopoulou, O. (2006). Bioorg. Med. Chem. 14, 6686–6694. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2005). SAINT-Plus and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cai, S. X. (2007). Recent Patents Anticancer Drug Discov. 2, 79–101. Google Scholar
Cai, S. X. (2008). Bioorg. Med. Chem. Lett. 18, 603–607. Web of Science PubMed Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Hyana, T. & Saimoto, H. (1987). Jpn Patent JP 621 812 768. Google Scholar
Sheldrick, G. M. (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, Q.-G., Wu, W.-Y., He, W., Sun, H.-S. & Guo, C. (2007). Acta Cryst. E63, o1437–o1438. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Valenti, P., Da Re, P., Rampa, A., Montanari, P., Carrara, M. & Cima, L. (1993). Anticancer Drug. Des. 8, 349–360. CAS PubMed Web of Science Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

rac-Ethyl 2-hy­dr­oxy-2,7,7-tri­methyl-4-(4-nitro­phen­yl)-5-oxo-3,4,5,6,7,8-hexa­hydro-2H-chromene-3-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

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