Ethyl 4-(5-bromo-2-hy­droxy­phen­yl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate

Kurbanova, M.M.; Huseynov, E.Z.; Gurbanov, A.V.; Maharramov, A.M.; Kia, R.

doi:10.1107/S1600536813006739

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o541

doi:10.1107/S1600536813006739

Open

access

Ethyl 4-(5-bromo-2-hydroxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate

Malahat M. Kurbanova,^a Elnur Z. Huseynov,^a Atash V. Gurbanov,^a ^* Abel M. Maharramov ^a and Reza Kia ^b,^c

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, ^bDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, and ^cStructural Dynamics of (Bio)Chemical Systems, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11, 37077 Göttingen, Germany
^*Correspondence e-mail: organik10@hotmail.com

(Received 4 March 2013; accepted 8 March 2013; online 16 March 2013)

In the title compound, C₂₁H₂₄BrNO₄, the dihedral angle between the heterocyclic ring and the pendant aromatic ring is 80.20 (13)°. The hexahydroquinone [i.e. the one with the C=O group] ring adopts a sofa conformation. An intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif. The ethyl group is disordered over two sets of sites with a refined site occupancy ratio of 0.633 (10):0.366 (10). In the crystal, molecules are linked by N—H⋯O interactions, forming chains parallel to [101]. There are no significant C—H⋯π or π–π interactions in the crystal structure.

Related literature

For standard bond lengths, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For background to hexahydroquinoline compounds and their applications, see: Sausins & Duburs (1988 ); Nakayama & Kasoaka (1996 ); Klusa (1995 ). For the synthesis of related compounds, see: Kumar et al. (2008 ); Song et al. (2012 ).

Experimental

Crystal data

C₂₁H₂₄BrNO₄
M_r = 434.32
Monoclinic, P 2₁ /n
a = 9.5969 (3) Å
b = 19.0805 (5) Å
c = 11.0678 (3) Å
β = 97.387 (1)°
V = 2009.84 (10) Å³
Z = 4
Mo Kα radiation
μ = 2.07 mm⁻¹
T = 294 K
0.24 × 0.22 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.636, T_max = 0.707
23241 measured reflections
5008 independent reflections
3604 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.136
S = 1.05
5008 reflections
266 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 1.10 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O1	0.88	1.75	2.625 (3)	171
N1—H1⋯O2ⁱ	0.86	2.05	2.866 (3)	158
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813006739/rz5051sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006739/rz5051Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813006739/rz5051Isup3.cml

checkCIF report

Comment top

Hexahydroquinoline derivatives possess a variety of biological activities, such as vasodilatory, bronchodilatory, antiatherosclerotic, hepatoprotective, and antidiabetic activity (Sausins et al., 1988), and some of them have been used as calcium channel modulators and curatives for cardiovascular diseases (Nakayama et al., 1996). In past years, their uses as neuroprotectants, platelet anti-aggregatory agents, and cerebral anti-ischemic agents in the treatment of Alzheimer's disease and as chemosensitizers in tumor therapy have been also reported (Klusa, 1995).

The asymmetric unit of the title compound, Fig. 1, comprises a substituted hexahydroquinoline compound. Both six-membered rings of the hexahydroquinoline ring system adopt a half-boat conformation. Bond lengths (Allen et al., 1987) and angles are within normal ranges. An intramolecular O—H···O hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure, molecules are linked together by intermolecular N—H···O hydrogen interactions (Table 1, Fig. 2) forming chains parallel to the [101] direction. The ethyl group is disordered over two sets of sites with a refined site occupancy ratio of 0.633 (10):0.366 (10). The compound contains one chiral center but the space group is centrosymmetric, so the molecule exists as a racemate.

Related literature top

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For background to hexahydroquinoline compounds and their applications, see: Sausins & Duburs (1988); Nakayama & Kasoaka (1996); Klusa (1995). For the synthesis of related compounds, see: Kumar et al. (2008); Song et al. (2012).

Experimental top

5-Bromsalicylaldehyde (0.201 g, 1 mmol), ethyl acetoacetate (0.25 ml, 1 mmol), dimedone (0.14 g, 1 mmol), ammonium acetate (0.116 g, 1.5 mmol) and ethanol (15 ml) were charged in a round bottom flask. Then the reaction mixture was stirred at room temperature for 12 hours, then the product was separated by filtration. Recrystallization was effected by using ethanol as solvent. Yield 86%. M. p. 520 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed down the b axis, showing the linkage of molecules through N—H···O hydrogen interactions (dashed lines). Only H atoms involved in hydrogen bonding are shown.

Ethyl 4-(5-bromo-2-hydroxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate top

Crystal data top

C₂₁H₂₄BrNO₄	F(000) = 896
M_r = 434.32	D_x = 1.435 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 520 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.5969 (3) Å	Cell parameters from 2045 reflections
b = 19.0805 (5) Å	θ = 3.3–27.5°
c = 11.0678 (3) Å	µ = 2.07 mm⁻¹
β = 97.387 (1)°	T = 294 K
V = 2009.84 (10) Å³	Block, colourless
Z = 4	0.24 × 0.22 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5008 independent reflections
Radiation source: fine-focus sealed tube	3604 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.636, T_max = 0.707	k = −25→25
23241 measured reflections	l = −14→14

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0542P)² + 1.4854P] where P = (F_o² + 2F_c²)/3
5008 reflections	(Δ/σ)_max = 0.001
266 parameters	Δρ_max = 1.10 e Å⁻³
3 restraints	Δρ_min = −1.02 e Å⁻³

Crystal data top

C₂₁H₂₄BrNO₄	V = 2009.84 (10) Å³
M_r = 434.32	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.5969 (3) Å	µ = 2.07 mm⁻¹
b = 19.0805 (5) Å	T = 294 K
c = 11.0678 (3) Å	0.24 × 0.22 × 0.18 mm
β = 97.387 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5008 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3604 reflections with I > 2σ(I)
T_min = 0.636, T_max = 0.707	R_int = 0.022
23241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	3 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.05	Δρ_max = 1.10 e Å⁻³
5008 reflections	Δρ_min = −1.02 e Å⁻³
266 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Br1	0.91668 (4)	0.11235 (2)	0.50601 (4)	0.09330 (19)
O1	0.4895 (3)	0.41833 (11)	0.5435 (2)	0.0719 (6)
O2	0.3062 (2)	0.18500 (11)	0.61555 (16)	0.0577 (5)
O3	0.3634 (2)	0.13165 (11)	0.79229 (19)	0.0597 (5)
O4	0.4398 (2)	0.31539 (12)	0.38649 (17)	0.0657 (6)
H4	0.4496	0.3478	0.4434	0.099*
N1	0.6847 (2)	0.28211 (11)	0.87199 (18)	0.0436 (5)
H1	0.7348	0.2820	0.9422	0.052*
C1	0.6826 (2)	0.34138 (12)	0.8040 (2)	0.0392 (5)
C2	0.7744 (3)	0.40011 (14)	0.8550 (2)	0.0487 (6)
H2A	0.8640	0.3812	0.8910	0.058*
H2B	0.7312	0.4228	0.9193	0.058*
C3	0.8001 (3)	0.45464 (14)	0.7599 (3)	0.0507 (6)
C4	0.6576 (3)	0.47395 (14)	0.6893 (3)	0.0584 (7)
H4A	0.6025	0.4986	0.7434	0.070*
H4B	0.6726	0.5057	0.6238	0.070*
C5	0.5754 (3)	0.41168 (14)	0.6362 (3)	0.0494 (6)
C6	0.5958 (2)	0.34543 (12)	0.6974 (2)	0.0385 (5)
C7	0.5182 (2)	0.28168 (12)	0.64397 (19)	0.0372 (5)
H7A	0.4239	0.2969	0.6095	0.045*
C8	0.5009 (2)	0.22835 (12)	0.74306 (19)	0.0350 (5)
C9	0.5861 (2)	0.22942 (13)	0.85029 (19)	0.0379 (5)
C10	0.5868 (3)	0.17973 (17)	0.9557 (2)	0.0576 (7)
H10A	0.5907	0.1324	0.9270	0.086*
H10B	0.5028	0.1862	0.9930	0.086*
H10C	0.6674	0.1889	1.0144	0.086*
C11	0.8970 (3)	0.42483 (18)	0.6729 (3)	0.0673 (8)
H11A	0.8543	0.3841	0.6329	0.101*
H11B	0.9855	0.4121	0.7182	0.101*
H11C	0.9120	0.4596	0.6132	0.101*
C12	0.8689 (4)	0.51939 (17)	0.8232 (4)	0.0734 (9)
H12A	0.8085	0.5383	0.8779	0.110*
H12B	0.8840	0.5540	0.7633	0.110*
H12C	0.9574	0.5065	0.8684	0.110*
C13	0.3830 (2)	0.18055 (13)	0.7107 (2)	0.0407 (5)
C14	0.2502 (7)	0.0825 (4)	0.7444 (6)	0.0617 (18)	0.633 (10)
H14A	0.2704	0.0612	0.6690	0.074*	0.633 (10)
H14B	0.1606	0.1066	0.7295	0.074*	0.633 (10)
C15	0.2477 (6)	0.0278 (4)	0.8428 (7)	0.080 (2)	0.633 (10)
H15A	0.1797	−0.0076	0.8157	0.120*	0.633 (10)
H15B	0.2229	0.0495	0.9154	0.120*	0.633 (10)
H15C	0.3389	0.0067	0.8599	0.120*	0.633 (10)
C14'	0.2263 (8)	0.0963 (5)	0.7967 (10)	0.051 (3)	0.367 (10)
H14C	0.1501	0.1219	0.7502	0.061*	0.367 (10)
H14D	0.2062	0.0910	0.8799	0.061*	0.367 (10)
C15'	0.2497 (11)	0.0255 (6)	0.7387 (15)	0.094 (5)	0.367 (10)
H15D	0.1635	−0.0007	0.7296	0.141*	0.367 (10)
H15E	0.3205	−0.0001	0.7899	0.141*	0.367 (10)
H15F	0.2798	0.0326	0.6602	0.141*	0.367 (10)
C16	0.5888 (3)	0.25025 (13)	0.5398 (2)	0.0407 (5)
C17	0.6996 (3)	0.20358 (14)	0.5642 (2)	0.0459 (6)
H17A	0.7331	0.1922	0.6444	0.055*
C18	0.7603 (3)	0.17389 (15)	0.4702 (3)	0.0561 (7)
C19	0.7115 (4)	0.18797 (18)	0.3507 (3)	0.0662 (9)
H19A	0.7507	0.1661	0.2881	0.079*
C20	0.6038 (4)	0.23495 (18)	0.3256 (2)	0.0643 (9)
H20A	0.5706	0.2451	0.2448	0.077*
C21	0.5431 (3)	0.26783 (15)	0.4182 (2)	0.0499 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0748 (3)	0.1056 (3)	0.1086 (4)	0.0222 (2)	0.0469 (2)	0.0037 (2)
O1	0.0849 (15)	0.0519 (12)	0.0703 (14)	0.0074 (11)	−0.0226 (12)	0.0177 (10)
O2	0.0550 (11)	0.0705 (13)	0.0419 (10)	−0.0123 (9)	−0.0152 (8)	0.0044 (9)
O3	0.0498 (11)	0.0594 (11)	0.0645 (12)	−0.0181 (9)	−0.0140 (9)	0.0208 (10)
O4	0.0744 (14)	0.0777 (14)	0.0404 (10)	−0.0011 (11)	−0.0102 (9)	0.0150 (10)
N1	0.0421 (10)	0.0523 (12)	0.0332 (9)	−0.0084 (9)	−0.0066 (8)	0.0074 (9)
C1	0.0378 (11)	0.0429 (12)	0.0373 (11)	−0.0015 (9)	0.0062 (9)	0.0009 (10)
C2	0.0483 (14)	0.0512 (15)	0.0459 (14)	−0.0081 (11)	0.0028 (11)	−0.0035 (11)
C3	0.0509 (14)	0.0430 (14)	0.0595 (16)	−0.0037 (11)	0.0123 (12)	−0.0006 (12)
C4	0.0626 (17)	0.0386 (14)	0.0738 (19)	0.0055 (12)	0.0078 (14)	0.0038 (13)
C5	0.0514 (15)	0.0432 (14)	0.0526 (15)	0.0085 (11)	0.0036 (12)	0.0053 (11)
C6	0.0399 (12)	0.0405 (12)	0.0349 (11)	0.0032 (9)	0.0040 (9)	0.0039 (9)
C7	0.0373 (11)	0.0447 (13)	0.0280 (10)	0.0021 (9)	−0.0024 (8)	0.0054 (9)
C8	0.0337 (10)	0.0426 (12)	0.0284 (10)	0.0016 (9)	0.0032 (8)	0.0042 (9)
C9	0.0373 (11)	0.0463 (13)	0.0298 (10)	−0.0021 (10)	0.0031 (8)	0.0047 (9)
C10	0.0631 (17)	0.0708 (18)	0.0352 (12)	−0.0208 (14)	−0.0084 (11)	0.0165 (12)
C11	0.0628 (18)	0.070 (2)	0.074 (2)	−0.0017 (15)	0.0281 (16)	0.0055 (16)
C12	0.075 (2)	0.0544 (18)	0.092 (2)	−0.0175 (16)	0.0133 (18)	−0.0061 (17)
C13	0.0382 (11)	0.0438 (13)	0.0388 (12)	0.0019 (10)	0.0002 (9)	0.0021 (10)
C14	0.061 (3)	0.065 (4)	0.055 (4)	−0.022 (3)	−0.004 (3)	0.005 (3)
C15	0.065 (3)	0.084 (4)	0.093 (5)	−0.018 (3)	0.012 (3)	0.028 (4)
C14'	0.047 (4)	0.062 (6)	0.044 (6)	−0.012 (4)	0.003 (4)	0.006 (4)
C15'	0.053 (5)	0.064 (7)	0.169 (16)	−0.009 (5)	0.025 (7)	−0.002 (8)
C16	0.0462 (13)	0.0448 (13)	0.0311 (11)	−0.0106 (10)	0.0046 (9)	0.0024 (10)
C17	0.0461 (13)	0.0529 (14)	0.0398 (12)	−0.0080 (11)	0.0102 (10)	0.0020 (11)
C18	0.0559 (15)	0.0575 (16)	0.0594 (17)	−0.0096 (13)	0.0248 (13)	−0.0029 (13)
C19	0.081 (2)	0.073 (2)	0.0509 (16)	−0.0240 (18)	0.0309 (15)	−0.0138 (15)
C20	0.081 (2)	0.083 (2)	0.0298 (12)	−0.0262 (18)	0.0102 (13)	−0.0010 (13)
C21	0.0578 (15)	0.0581 (16)	0.0328 (12)	−0.0163 (13)	0.0022 (10)	0.0049 (11)

Geometric parameters (Å, º) top

Br1—C18	1.907 (3)	C10—H10A	0.9600
O1—C5	1.238 (3)	C10—H10B	0.9600
O2—C13	1.208 (3)	C10—H10C	0.9600
O3—C13	1.329 (3)	C11—H11A	0.9600
O3—C14	1.481 (5)	C11—H11B	0.9600
O3—C14'	1.485 (7)	C11—H11C	0.9600
O4—C21	1.357 (4)	C12—H12A	0.9600
O4—H4	0.8798	C12—H12B	0.9600
N1—C1	1.357 (3)	C12—H12C	0.9600
N1—C9	1.381 (3)	C14—C15	1.512 (4)
N1—H1	0.8600	C14—H14A	0.9700
C1—C6	1.356 (3)	C14—H14B	0.9700
C1—C2	1.491 (3)	C15—H15A	0.9600
C2—C3	1.523 (4)	C15—H15B	0.9600
C2—H2A	0.9700	C15—H15C	0.9600
C2—H2B	0.9700	C14'—C15'	1.526 (5)
C3—C12	1.528 (4)	C14'—H14C	0.9700
C3—C4	1.530 (4)	C14'—H14D	0.9700
C3—C11	1.531 (4)	C15'—H15D	0.9600
C4—C5	1.503 (4)	C15'—H15E	0.9600
C4—H4A	0.9700	C15'—H15F	0.9600
C4—H4B	0.9700	C16—C17	1.386 (4)
C5—C6	1.436 (3)	C16—C21	1.402 (3)
C6—C7	1.507 (3)	C17—C18	1.378 (4)
C7—C8	1.521 (3)	C17—H17A	0.9300
C7—C16	1.532 (3)	C18—C19	1.371 (4)
C7—H7A	0.9800	C19—C20	1.369 (5)
C8—C9	1.352 (3)	C19—H19A	0.9300
C8—C13	1.461 (3)	C20—C21	1.392 (4)
C9—C10	1.503 (3)	C20—H20A	0.9300

C13—O3—C14	111.3 (3)	C3—C11—H11A	109.5
C13—O3—C14'	123.0 (5)	C3—C11—H11B	109.5
C21—O4—H4	106.1	H11A—C11—H11B	109.5
C1—N1—C9	123.33 (19)	C3—C11—H11C	109.5
C1—N1—H1	118.0	H11A—C11—H11C	109.5
C9—N1—H1	116.5	H11B—C11—H11C	109.5
C6—C1—N1	119.6 (2)	C3—C12—H12A	109.5
C6—C1—C2	123.6 (2)	C3—C12—H12B	109.5
N1—C1—C2	116.8 (2)	H12A—C12—H12B	109.5
C1—C2—C3	113.1 (2)	C3—C12—H12C	109.5
C1—C2—H2A	109.0	H12A—C12—H12C	109.5
C3—C2—H2A	109.0	H12B—C12—H12C	109.5
C1—C2—H2B	109.0	O2—C13—O3	121.2 (2)
C3—C2—H2B	109.0	O2—C13—C8	122.4 (2)
H2A—C2—H2B	107.8	O3—C13—C8	116.37 (19)
C2—C3—C12	109.5 (2)	O3—C14—C15	105.0 (4)
C2—C3—C4	107.7 (2)	O3—C14—H14A	110.8
C12—C3—C4	110.2 (2)	C15—C14—H14A	110.8
C2—C3—C11	110.2 (2)	O3—C14—H14B	110.8
C12—C3—C11	109.1 (3)	C15—C14—H14B	110.8
C4—C3—C11	110.1 (3)	H14A—C14—H14B	108.8
C5—C4—C3	113.5 (2)	O3—C14'—C15'	102.1 (6)
C5—C4—H4A	108.9	O3—C14'—H14C	111.4
C3—C4—H4A	108.9	C15'—C14'—H14C	111.4
C5—C4—H4B	108.9	O3—C14'—H14D	111.4
C3—C4—H4B	108.9	C15'—C14'—H14D	111.4
H4A—C4—H4B	107.7	H14C—C14'—H14D	109.2
O1—C5—C6	121.2 (3)	C14'—C15'—H15D	109.5
O1—C5—C4	120.2 (2)	C14'—C15'—H15E	109.5
C6—C5—C4	118.6 (2)	H15D—C15'—H15E	109.5
C1—C6—C5	119.5 (2)	C14'—C15'—H15F	109.5
C1—C6—C7	120.9 (2)	H15D—C15'—H15F	109.5
C5—C6—C7	119.7 (2)	H15E—C15'—H15F	109.5
C6—C7—C8	110.56 (18)	C17—C16—C21	118.5 (2)
C6—C7—C16	111.54 (19)	C17—C16—C7	120.5 (2)
C8—C7—C16	112.36 (19)	C21—C16—C7	121.0 (2)
C6—C7—H7A	107.4	C18—C17—C16	120.4 (2)
C8—C7—H7A	107.4	C18—C17—H17A	119.8
C16—C7—H7A	107.4	C16—C17—H17A	119.8
C9—C8—C13	125.9 (2)	C19—C18—C17	121.5 (3)
C9—C8—C7	120.9 (2)	C19—C18—Br1	118.9 (2)
C13—C8—C7	113.17 (18)	C17—C18—Br1	119.6 (2)
C8—C9—N1	119.2 (2)	C20—C19—C18	118.7 (3)
C8—C9—C10	127.9 (2)	C20—C19—H19A	120.7
N1—C9—C10	112.93 (19)	C18—C19—H19A	120.7
C9—C10—H10A	109.5	C19—C20—C21	121.5 (3)
C9—C10—H10B	109.5	C19—C20—H20A	119.3
H10A—C10—H10B	109.5	C21—C20—H20A	119.3
C9—C10—H10C	109.5	O4—C21—C20	118.2 (2)
H10A—C10—H10C	109.5	O4—C21—C16	122.4 (2)
H10B—C10—H10C	109.5	C20—C21—C16	119.4 (3)

C9—N1—C1—C6	−11.6 (4)	C1—N1—C9—C8	14.5 (4)
C9—N1—C1—C2	166.2 (2)	C1—N1—C9—C10	−164.2 (2)
C6—C1—C2—C3	−19.6 (4)	C14—O3—C13—O2	6.0 (5)
N1—C1—C2—C3	162.7 (2)	C14'—O3—C13—O2	−21.9 (6)
C1—C2—C3—C12	168.6 (2)	C14—O3—C13—C8	−174.5 (4)
C1—C2—C3—C4	48.8 (3)	C14'—O3—C13—C8	157.6 (5)
C1—C2—C3—C11	−71.4 (3)	C9—C8—C13—O2	175.8 (2)
C2—C3—C4—C5	−53.9 (3)	C7—C8—C13—O2	−1.8 (3)
C12—C3—C4—C5	−173.3 (3)	C9—C8—C13—O3	−3.7 (4)
C11—C3—C4—C5	66.4 (3)	C7—C8—C13—O3	178.8 (2)
C3—C4—C5—O1	−152.6 (3)	C13—O3—C14—C15	176.1 (5)
C3—C4—C5—C6	29.2 (4)	C14'—O3—C14—C15	−62.6 (10)
N1—C1—C6—C5	169.3 (2)	C13—O3—C14'—C15'	102.7 (10)
C2—C1—C6—C5	−8.3 (4)	C14—O3—C14'—C15'	31.1 (9)
N1—C1—C6—C7	−9.4 (3)	C6—C7—C16—C17	84.8 (3)
C2—C1—C6—C7	173.0 (2)	C8—C7—C16—C17	−40.0 (3)
O1—C5—C6—C1	−174.8 (3)	C6—C7—C16—C21	−95.2 (3)
C4—C5—C6—C1	3.3 (4)	C8—C7—C16—C21	140.0 (2)
O1—C5—C6—C7	3.9 (4)	C21—C16—C17—C18	−1.8 (4)
C4—C5—C6—C7	−178.0 (2)	C7—C16—C17—C18	178.2 (2)
C1—C6—C7—C8	24.1 (3)	C16—C17—C18—C19	−1.6 (4)
C5—C6—C7—C8	−154.6 (2)	C16—C17—C18—Br1	177.85 (19)
C1—C6—C7—C16	−101.7 (2)	C17—C18—C19—C20	2.8 (4)
C5—C6—C7—C16	79.6 (3)	Br1—C18—C19—C20	−176.7 (2)
C6—C7—C8—C9	−21.1 (3)	C18—C19—C20—C21	−0.5 (5)
C16—C7—C8—C9	104.2 (2)	C19—C20—C21—O4	178.0 (3)
C6—C7—C8—C13	156.56 (19)	C19—C20—C21—C16	−2.8 (4)
C16—C7—C8—C13	−78.1 (2)	C17—C16—C21—O4	−177.0 (2)
C13—C8—C9—N1	−173.8 (2)	C7—C16—C21—O4	3.1 (4)
C7—C8—C9—N1	3.6 (3)	C17—C16—C21—C20	3.9 (4)
C13—C8—C9—C10	4.8 (4)	C7—C16—C21—C20	−176.0 (2)
C7—C8—C9—C10	−177.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1	0.88	1.75	2.625 (3)	171
N1—H1···O2ⁱ	0.86	2.05	2.866 (3)	158

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄BrNO₄
M_r	434.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	9.5969 (3), 19.0805 (5), 11.0678 (3)
β (°)	97.387 (1)
V (Å³)	2009.84 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.07
Crystal size (mm)	0.24 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.636, 0.707
No. of measured, independent and observed [I > 2σ(I)] reflections	23241, 5008, 3604
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.136, 1.05
No. of reflections	5008
No. of parameters	266
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.10, −1.02

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O1	0.88	1.75	2.625 (3)	171
N1—H1···O2ⁱ	0.86	2.05	2.866 (3)	158

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

Acknowledgements

The authors thank the Chemistry Department, Baku State University, for providing the X-ray diffraction facility.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Klusa, V. (1995). Drugs Future, 20, 135–138. Google Scholar
Kumar, S., Sharma, P., Kapoor, K. K. & Hundal, M. S. (2008). Tetrahedron, 64, 536–542. Web of Science CSD CrossRef CAS Google Scholar
Nakayama, H. & Kasoaka, Y. (1996). Heterocycles, 42, 901–909. CrossRef CAS Google Scholar
Sausins, A. & Duburs, G. (1988). Heterocycles, 27, 269–289. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, S. J., Shan, Z. X. & Jin, J. (2012). Synth. Commun. 40, 3067–3077. Web of Science CSD CrossRef Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o541

doi:10.1107/S1600536813006739

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Ethyl 4-(5-bromo-2-hy­dr­oxy­phen­yl)-2,7,7-tri­methyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl 4-(5-bromo-2-hydroxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate