Ethyle 4-bromo-3-hydr­oxy-5,6,7,8-tétrahydro­naphtalène-2-carboxyl­ate

In the title compound, C₁₃H₁₅BrO₃, all non-H atoms lie on a mirror plane, except for two CH₂ groups which are disordered equally on the two sides of the plane.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.047
• wR factor = 0.120
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.72
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C6
PLAT301_ALERT_3_C Main Residue  Disorder .........................      11.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      20.00 Deg.
              C6   -C5   -C6      6.565   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      41.40 Deg.
              C7   -C8   -C7      6.565   1.555   1.555

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.723
            Tmax scaled      0.723 Tmin scaled      0.410

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Les esters du 4-bromo-3-hydroxynaphtalène ont été rarement étudiés bien qu'ils soient à la base de composés à intérêt biologique (Kasibhatla et al., 2001).

La molécule C₁₃H₁₅BrO₃ est caracterisée par la présence d'un noyau 5,6,7,8 - tétrahydronaphtalène ayant le groupe phényle trisubstitué en C2, C3 et C4 portant respectivement une fonction ester, un groupe hydroxyle et un atome de brome (Fig. 1). Ces trois derniers substituants et le noyau phényle sont situés dans un plan miroir. Les atomes de carbone C5, C8, C9 et C10 sont situés dans ce plan miroir. Les atomes de carbone C6 et C7 sont statistiquement distribués par rapport à ce plan cristallographique. Les valeurs des longueurs des liaisions C4—Br1 (1,908 (5) Å), C11═O1 (1,217 (6) Å) et la valeur moyenne des distances C—O (1,381 (7) Å) sont en accord avec celles des composés possédant des liaisons de ce type (Ben Amor & Jouini, 1999; Canty et al., 2004; Béji et al., 2005).

Related literature

Pour le contexte général du travail, voir: Kasibhatla et al. (2001). Pour structures associées, voir: Ben Amor & Jouini, 1999; Canty et al., 2004; Béji et al., 2005.

S2. Experimental

A une solution de 3-hydroxy-5,6,7,8 - tétrahydronaphtalène-2-carboxylate d'éthyle (2 mmol) dans 2 ml d'acide acétique est ajoutée goutte-à -goutte une solution de brome (2 mmol) dans 2 ml d'acide acétique sous agitation magnétique, à température ambiante. Après deux heures, le mélange résultant a été dilué dans l'eau et extrait avec du dichlorométhane. La phase organique a été lavée avec de l'eau jusqu'á neutralité. Le résidu a été purifié sur une colonne de chromatographie (éther de pétrole) pour obtenir á l'état très pur le 4-bromo-3-hydroxy-5,6,7,8 - tétrahydronaphtalène-2-carboxylate d'éthyle.

S3. Refinement

L'ensemble des atomes d'hydrogène ont été fixés géométriquement et traités en utilisant un `riding model' avec des distances C—H = 0.93 Å (C_aromatique), 0.97 Å (C_methylène), 0.96 Å (CH₃) et O—H = 0.82 Å avec des facteurs de température U_iso(H) = 1.2U_eq(C_aromatique, C_methylène, O) et U_iso(H) = 1.5U_eq(CH₃).

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Représentation de la molécule C13H15BrO3. Les ellipsoides d'agitation thermique représentent 30% de probabilité de présence.

Ethyl 4-bromo-3-hydroxy-5,6,7,8-tetrahydronaphthalene-2-carboxylate

Crystal data

C13H15BrO3	F(000) = 608
Mr = 299.16	Dx = 1.570 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 25 reflections
a = 20.840 (6) Å	θ = 10.5–14.7°
b = 7.141 (3) Å	µ = 3.24 mm^−1
c = 9.364 (3) Å	T = 298 K
β = 114.77 (3)°	Plate, colourless
V = 1265.3 (8) Å^3	0.40 × 0.10 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1070 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 27.0°, θmin = 2.2°
ω/2θ scans	h = −26→24
Absorption correction: ψ scan (North et al., 1968)	k = −1→9
Tmin = 0.567, Tmax = 1.000	l = 0→11
3614 measured reflections	2 standard reflections every 120 min
1483 independent reflections	intensity decay: 4%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 1.9759P] where P = (Fo^2 + 2Fc^2)/3
1483 reflections	(Δ/σ)max = 0.002
109 parameters	Δρmax = 0.59 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.59010 (3)	0.5000	0.98075 (8)	0.0748 (3)
O1	0.8758 (2)	0.5000	1.3330 (4)	0.0636 (10)
O2	0.92499 (17)	0.5000	1.1618 (4)	0.0572 (9)
O3	0.7377 (2)	0.5000	1.2234 (4)	0.0630 (10)
H3	0.7785	0.5000	1.2911	0.076*
C1	0.7968 (2)	0.5000	0.9059 (5)	0.0468 (11)
H1	0.8385	0.5000	0.8924	0.056*
C2	0.8008 (2)	0.5000	1.0587 (5)	0.0417 (10)
C3	0.7380 (3)	0.5000	1.0790 (5)	0.0449 (11)
C4	0.6740 (2)	0.5000	0.9467 (6)	0.0445 (11)
C5	0.5989 (2)	0.5000	0.6514 (6)	0.0544 (12)
H5A	0.5761	0.3798	0.6447	0.065*	0.50
H5B	0.5689	0.5955	0.6655	0.065*	0.50
C6	0.6056 (4)	0.536 (5)	0.4988 (8)	0.084 (10)	0.50
H6A	0.5871	0.4255	0.4348	0.101*	0.50
H6B	0.5726	0.6367	0.4470	0.101*	0.50
C7	0.6621 (3)	0.5774 (12)	0.4855 (7)	0.062 (2)	0.50
H7A	0.6656	0.7128	0.4853	0.074*	0.50
H7B	0.6572	0.5338	0.3834	0.074*	0.50
C8	0.7335 (3)	0.5000	0.6118 (6)	0.0624 (15)
H8A	0.7408	0.3734	0.5841	0.075*	0.50
H8B	0.7722	0.5770	0.6136	0.075*	0.50
C9	0.7332 (2)	0.5000	0.7743 (5)	0.0432 (10)
C10	0.6699 (2)	0.5000	0.7937 (5)	0.0422 (10)
C11	0.8699 (3)	0.5000	1.1980 (6)	0.0492 (11)
C12	0.9947 (3)	0.5000	1.2930 (6)	0.0611 (14)
H12A	1.0005	0.3897	1.3578	0.073*	0.50
H12B	1.0005	0.6103	1.3578	0.073*	0.50
C13	1.0479 (3)	0.5000	1.2249 (7)	0.085 (2)
H13A	1.0946	0.5000	1.3084	0.127*
H13B	1.0416	0.6098	1.1613	0.127*	0.50
H13C	1.0416	0.3902	1.1613	0.127*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0585 (4)	0.0930 (5)	0.0924 (5)	0.000	0.0507 (3)	0.000
O1	0.066 (2)	0.083 (3)	0.0402 (18)	0.000	0.0209 (17)	0.000
O2	0.0413 (17)	0.083 (3)	0.0418 (18)	0.000	0.0119 (14)	0.000
O3	0.067 (2)	0.080 (3)	0.054 (2)	0.000	0.0383 (18)	0.000
C1	0.041 (2)	0.055 (3)	0.047 (2)	0.000	0.020 (2)	0.000
C2	0.047 (2)	0.038 (2)	0.042 (2)	0.000	0.021 (2)	0.000
C3	0.056 (3)	0.034 (2)	0.054 (3)	0.000	0.032 (2)	0.000
C4	0.043 (2)	0.038 (2)	0.061 (3)	0.000	0.031 (2)	0.000
C5	0.035 (2)	0.060 (3)	0.066 (3)	0.000	0.018 (2)	0.000
C6	0.049 (4)	0.13 (3)	0.054 (4)	0.023 (9)	0.006 (3)	0.021 (9)
C7	0.051 (4)	0.085 (6)	0.042 (3)	0.000 (4)	0.013 (3)	0.002 (3)
C8	0.048 (3)	0.099 (4)	0.040 (2)	0.000	0.018 (2)	0.000
C9	0.040 (2)	0.049 (3)	0.043 (2)	0.000	0.020 (2)	0.000
C10	0.040 (2)	0.034 (2)	0.054 (3)	0.000	0.021 (2)	0.000
C11	0.054 (3)	0.047 (3)	0.045 (3)	0.000	0.019 (2)	0.000
C12	0.048 (3)	0.082 (4)	0.042 (3)	0.000	0.008 (2)	0.000
C13	0.045 (3)	0.140 (7)	0.058 (3)	0.000	0.011 (3)	0.000

Geometric parameters (Å, º)

Br1—C4	1.905 (4)	C6—C7	1.268 (12)
O1—C11	1.218 (6)	C6—H6A	0.9700
O2—C11	1.327 (6)	C6—H6B	0.9700
O2—C12	1.457 (6)	C7—C8	1.563 (8)
O3—C3	1.356 (5)	C7—H7A	0.9700
O3—H3	0.8200	C7—H7B	0.9700
C1—C9	1.380 (7)	C8—C9	1.525 (6)
C1—C2	1.397 (6)	C8—C7^i	1.563 (8)
C1—H1	0.9300	C8—H8A	0.9700
C2—C3	1.399 (6)	C8—H8B	0.9700
C2—C11	1.483 (7)	C9—C10	1.405 (6)
C3—C4	1.388 (7)	C12—C13	1.492 (8)
C4—C10	1.399 (6)	C12—H12A	0.9700
C5—C6^i	1.516 (10)	C12—H12B	0.9700
C5—C6	1.516 (10)	C13—H13A	0.9600
C5—C10	1.520 (7)	C13—H13B	0.9600
C5—H5A	0.9700	C13—H13C	0.9600
C5—H5B	0.9700
C11—O2—C12	116.7 (4)	C8—C7—H7B	107.8
C3—O3—H3	109.5	H7A—C7—H7B	107.1
C9—C1—C2	122.6 (4)	C9—C8—C7^i	110.7 (4)
C9—C1—H1	118.7	C9—C8—C7	110.7 (4)
C2—C1—H1	118.7	C7^i—C8—C7	41.4 (6)
C1—C2—C3	118.7 (4)	C9—C8—H8A	109.5
C1—C2—C11	121.4 (4)	C7^i—C8—H8A	71.0
C3—C2—C11	119.9 (4)	C7—C8—H8A	109.5
O3—C3—C4	119.0 (4)	C9—C8—H8B	109.5
O3—C3—C2	122.1 (4)	C7^i—C8—H8B	137.3
C4—C3—C2	118.8 (4)	C7—C8—H8B	109.5
C3—C4—C10	122.5 (4)	H8A—C8—H8B	108.1
C3—C4—Br1	117.2 (3)	C1—C9—C10	119.1 (4)
C10—C4—Br1	120.3 (3)	C1—C9—C8	119.2 (4)
C6^i—C5—C6	20 (3)	C10—C9—C8	121.7 (4)
C6^i—C5—C10	112.7 (4)	C4—C10—C9	118.3 (4)
C6—C5—C10	112.7 (4)	C4—C10—C5	121.2 (4)
C6^i—C5—H5A	91.3	C9—C10—C5	120.6 (4)
C6—C5—H5A	109.1	O1—C11—O2	122.9 (5)
C10—C5—H5A	109.1	O1—C11—C2	123.5 (5)
C6^i—C5—H5B	124.6	O2—C11—C2	113.6 (4)
C6—C5—H5B	109.1	O2—C12—C13	107.2 (4)
C10—C5—H5B	109.1	O2—C12—H12A	110.3
H5A—C5—H5B	107.8	C13—C12—H12A	110.3
C7—C6—C5	126.0 (6)	O2—C12—H12B	110.3
C7—C6—H6A	105.8	C13—C12—H12B	110.3
C5—C6—H6A	105.8	H12A—C12—H12B	108.5
C7—C6—H6B	105.8	C12—C13—H13A	109.5
C5—C6—H6B	105.8	C12—C13—H13B	109.5
H6A—C6—H6B	106.2	H13A—C13—H13B	109.5
C6—C7—C8	118.2 (11)	C12—C13—H13C	109.5
C6—C7—H7A	107.8	H13A—C13—H13C	109.5
C8—C7—H7A	107.8	H13B—C13—H13C	109.5
C6—C7—H7B	107.8

Symmetry code: (i) x, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.82	1.90	2.620 (5)	146