Ethyl anthracene-9-carboxyl­ate

Weber, E.; Seichter, W.; Fischer, C.; Bendrath, L.M.S.F.; Ibragimov, B.T.

doi:10.1107/S1600536808017819

organic compounds

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Volume 64| Part 7| July 2008| Page o1288

doi:10.1107/S1600536808017819

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Ethyl anthracene-9-carboxylate

Edwin Weber,^a Wilhelm Seichter,^a Conrad Fischer,^a L. M. S. Franziska Bendrath ^a and Bakhtiyar T. Ibragimov ^b ^*

^aInstitut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany, and ^bInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, H Abdullaev 83, Tashkent 100125, Uzbekistan
^*Correspondence e-mail: bahtier@academy.uzsci.net

(Received 28 April 2008; accepted 12 June 2008; online 19 June 2008)

In the title compound, C₁₇H₁₄O₂, the COO group and the anthracene fragment form a dihedral angle of 76.00 (19)°. The torsion angle around the O—Csp³ bond of the ester group is 108.52 (18)°. The crystal structure is stabilized by C—H⋯O interactions and edge-to-face arene interactions with C—H⋯(ring centroid) distances in the range 2.75–2.84 Å.

Related literature

For related crystal structures, see: Bart & Schmidt (1971 ); Heller & Schmidt (1971 ); Sweeting et al. (1997 ). For the preparation of the title compound, see: Larsen & Harpp (1980 ).

Experimental

Crystal data

C₁₇H₁₄O₂
M_r = 250.28
Orthorhombic, P n a 2₁
a = 8.5431 (6) Å
b = 10.2137 (7) Å
c = 14.5426 (11) Å
V = 1268.94 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 153 (2) K
0.25 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: none
15373 measured reflections
2020 independent reflections
1600 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.085
S = 1.04
2020 reflections
174 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.93	2.53	3.302 (2)	140
Symmetry code: (i) $[-x, -y+2, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017819/gk2145sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017819/gk2145Isup2.hkl

checkCIF report

Comment top

9-Anthracenecarboxylic acid esters are of current interest in materials science (Sweeting et al., 1997). The conformational features of the title compound (Fig. 1) resemble those found in the crystal structure of the analogous methyl 9-anthracenecarboxylate (Bart & Schmidt, 1971). A comparative examination of the crystal structures, however, reveals that a slight modification of the molecular structure has a fundamental influence on the molecular packing mode. According to the presence of a twofold screw axis, helical hydrogen bonded strands (Table 1, Fig. 2) running along the c axis are the basic supramolecular entities of the present crystal structure. Furthermore, the anthracene units of neighbouring strands are arranged in "edge-to-face" herringbone fashion with the closest intermolecular distance of 2.86 Å.

Related literature top

For related crystal structures, see: Bart & Schmidt (1971); Heller & Schmidt (1971); Sweeting et al. (1997). For the preparation of the title compound, see: Larsen & Harpp (1980).

Experimental top

9-Anthracenecarbonyl chloride (300 mg) in CH₂Cl₂ (45 ml) was reacted with ethanol (10 ml) and pyridine (2 ml). The resulting solution was heated under reflux for 11 h, then cooled to room temperature and subsequently extracted three times with 2 N aqueous HCl and water (50 ml, each), and finally two times with water (100 ml). After addition of CH₂Cl₂ (200 ml) the organic layer was dried over CaCl₂ and the solvent removed under reduced pressure. Recrystallization of the white powder from acetone yielded colourless crystals suitable for X-ray diffraction analysis. (82%, m.p. 381–382 K). Anal. Calcd. for C₁₇H₁₄O₂: C 81.58; H 5.64; Found: C 81.42; H 5.90%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with atomic labels and 50% probability displacement ellipsoids for non H-atoms.
	Fig. 2. Crystal packing of the title compound viewed along the b axis.

Ethyl anthracene-9-carboxylate top

Crystal data top

C₁₇H₁₄O₂	F(000) = 528
M_r = 250.28	D_x = 1.310 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4881 reflections
a = 8.5431 (6) Å	θ = 2.4–30.5°
b = 10.2137 (7) Å	µ = 0.09 mm⁻¹
c = 14.5426 (11) Å	T = 153 K
V = 1268.94 (16) Å³	Irregular, colourless
Z = 4	0.25 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 30.6°, θ_min = 2.4°
ϕ and ω scans	h = −11→12
15373 measured reflections	k = −12→14
2020 independent reflections	l = −20→13

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0459P)²] where P = (F_o² + 2F_c²)/3
2020 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.22 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₇H₁₄O₂	V = 1268.94 (16) Å³
M_r = 250.28	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 8.5431 (6) Å	µ = 0.09 mm⁻¹
b = 10.2137 (7) Å	T = 153 K
c = 14.5426 (11) Å	0.25 × 0.25 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1600 reflections with I > 2σ(I)
15373 measured reflections	R_int = 0.047
2020 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.085	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
2020 reflections	Δρ_min = −0.17 e Å⁻³
174 parameters

Special details top

Experimental. ¹H-NMR (400 MHz, CDCl₃, δ, p.p.m.): 1.53 (m, CH₃); 4.68 (q, ³J=7.2 Hz, OCH₂, 2H); 7.45 (m, H₂, H₃, H₆, H₇, 4H); 8.03 (t, H₁, H₄, H₅, H₈, 4H); 8.54 (t, H₁₀, 1H). ¹³C-NMR (100 MHz, CDCl₃, δ, p.p.m.): 13.70 (CH₃), 61.70 (OCH₂), 125.17 (C₁, C₈), 125.86 (C₃, C₆), 127.25 (C₂, C₇); 128.37 (C₉, C_4a, C₁₀_a); 128.89 (C₄, C₅); 129.23 (C₁₀); 131.35 (C_8a, C_9a); 169.10 (CŌ). IR (KBr, cm^-1): 3079 (w), 3053 (w)(C–H_ar); 2981 (m), 2929, 2904, 2867 (C–H); 1952; 1802; 1715 (C?O); 1626; 1564; 1522; 1467; 1455; 1420; 1388; 1372; 1352; 1321; 1288; 1264; 1238; 1216; 1171; 1151; 1119; 1099; 1025; 974; 957; 935; 897; 866; 846; 810; 740; 671; 633; 607; 560; 529; 452. GC—MS m/z 250 (100, M⁺), 235, 222, 205, 177, 151, 139, 126, 102, 88, 75, 51.

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.13453 (17)	0.82389 (13)	−0.03306 (11)	0.0430 (4)
O2	0.30770 (15)	0.75339 (12)	0.07149 (10)	0.0316 (3)
C1	0.28393 (19)	0.97928 (15)	0.05261 (11)	0.0195 (3)
C2	0.23153 (19)	1.03155 (15)	0.13680 (11)	0.0198 (3)
C3	0.1270 (2)	0.96373 (17)	0.19647 (11)	0.0233 (4)
H3	0.0919	0.8805	0.1806	0.028*
C4	0.0777 (2)	1.01972 (17)	0.27676 (12)	0.0264 (4)
H4	0.0082	0.9747	0.3145	0.032*
C5	0.1310 (2)	1.14542 (18)	0.30335 (12)	0.0269 (4)
H5	0.0973	1.1818	0.3585	0.032*
C6	0.2313 (2)	1.21299 (17)	0.24865 (12)	0.0249 (4)
H6	0.2662	1.2951	0.2672	0.030*
C7	0.2840 (2)	1.16012 (15)	0.16313 (11)	0.0206 (3)
C8	0.3840 (2)	1.22952 (16)	0.10477 (12)	0.0222 (3)
H8	0.4185	1.3121	0.1226	0.027*
C9	0.4334 (2)	1.17882 (15)	0.02076 (11)	0.0210 (3)
C10	0.5365 (2)	1.24932 (16)	−0.03850 (12)	0.0269 (4)
H10	0.5701	1.3325	−0.0216	0.032*
C11	0.5865 (2)	1.19688 (18)	−0.11930 (14)	0.0307 (4)
H11	0.6544	1.2441	−0.1567	0.037*
C12	0.5355 (2)	1.07060 (19)	−0.14688 (12)	0.0294 (4)
H12	0.5700	1.0358	−0.2024	0.035*
C13	0.4366 (2)	1.00008 (16)	−0.09291 (11)	0.0256 (4)
H13	0.4040	0.9176	−0.1122	0.031*
C14	0.38172 (19)	1.05069 (16)	−0.00681 (11)	0.0201 (3)
C15	0.2313 (2)	0.84551 (16)	0.02446 (12)	0.0224 (3)
C16	0.2630 (2)	0.61657 (16)	0.05647 (15)	0.0336 (4)
H16A	0.3556	0.5640	0.0454	0.040*
H16B	0.1954	0.6100	0.0031	0.040*
C17	0.1792 (2)	0.56759 (19)	0.13964 (15)	0.0366 (5)
H17A	0.2438	0.5802	0.1929	0.055*
H17B	0.1569	0.4760	0.1324	0.055*
H17C	0.0830	0.6150	0.1471	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0469 (9)	0.0323 (8)	0.0498 (9)	−0.0006 (6)	−0.0262 (8)	−0.0080 (6)
O2	0.0389 (8)	0.0185 (5)	0.0374 (7)	−0.0030 (5)	−0.0137 (6)	−0.0007 (5)
C1	0.0205 (8)	0.0176 (7)	0.0204 (7)	0.0016 (6)	−0.0040 (6)	−0.0016 (6)
C2	0.0201 (8)	0.0202 (7)	0.0192 (7)	0.0007 (6)	−0.0040 (6)	0.0016 (6)
C3	0.0239 (9)	0.0218 (8)	0.0243 (9)	−0.0021 (6)	−0.0015 (7)	0.0004 (6)
C4	0.0260 (9)	0.0292 (9)	0.0239 (8)	−0.0010 (7)	0.0038 (7)	0.0037 (7)
C5	0.0303 (10)	0.0298 (9)	0.0204 (8)	0.0032 (7)	0.0022 (7)	−0.0041 (7)
C6	0.0293 (10)	0.0210 (8)	0.0245 (8)	0.0005 (7)	−0.0007 (8)	−0.0047 (7)
C7	0.0220 (9)	0.0190 (7)	0.0208 (7)	0.0012 (6)	−0.0019 (6)	−0.0014 (6)
C8	0.0241 (9)	0.0190 (8)	0.0235 (8)	−0.0008 (6)	−0.0015 (7)	−0.0016 (6)
C9	0.0203 (8)	0.0203 (7)	0.0225 (7)	0.0015 (6)	−0.0011 (7)	0.0012 (6)
C10	0.0262 (10)	0.0257 (8)	0.0289 (9)	−0.0027 (7)	−0.0001 (7)	0.0017 (7)
C11	0.0293 (10)	0.0337 (10)	0.0292 (9)	−0.0003 (8)	0.0066 (8)	0.0068 (8)
C12	0.0298 (10)	0.0361 (10)	0.0222 (8)	0.0067 (8)	0.0039 (7)	−0.0006 (7)
C13	0.0286 (10)	0.0246 (8)	0.0235 (8)	0.0021 (7)	−0.0007 (7)	−0.0039 (6)
C14	0.0198 (8)	0.0206 (7)	0.0200 (8)	0.0025 (6)	−0.0021 (6)	−0.0014 (6)
C15	0.0232 (9)	0.0235 (7)	0.0205 (7)	−0.0007 (6)	0.0009 (7)	−0.0026 (7)
C16	0.0422 (11)	0.0181 (8)	0.0407 (10)	−0.0045 (7)	−0.0063 (9)	−0.0034 (7)
C17	0.0353 (11)	0.0302 (10)	0.0443 (11)	−0.0068 (8)	−0.0071 (9)	0.0026 (9)

Geometric parameters (Å, º) top

O1—C15	1.197 (2)	C8—H8	0.9300
O2—C15	1.334 (2)	C9—C10	1.427 (2)
O2—C16	1.465 (2)	C9—C14	1.438 (2)
C1—C14	1.406 (2)	C10—C11	1.360 (3)
C1—C2	1.409 (2)	C10—H10	0.9300
C1—C15	1.495 (2)	C11—C12	1.419 (3)
C2—C3	1.425 (2)	C11—H11	0.9300
C2—C7	1.439 (2)	C12—C13	1.360 (3)
C3—C4	1.367 (2)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.433 (2)
C4—C5	1.416 (3)	C13—H13	0.9300
C4—H4	0.9300	C16—C17	1.492 (3)
C5—C6	1.357 (3)	C16—H16A	0.9700
C5—H5	0.9300	C16—H16B	0.9700
C6—C7	1.429 (2)	C17—H17A	0.9600
C6—H6	0.9300	C17—H17B	0.9600
C7—C8	1.397 (2)	C17—H17C	0.9600
C8—C9	1.393 (2)

C15—O2—C16	117.96 (15)	C11—C10—H10	119.4
C14—C1—C2	121.76 (14)	C9—C10—H10	119.4
C14—C1—C15	118.97 (15)	C10—C11—C12	120.39 (17)
C2—C1—C15	119.25 (15)	C10—C11—H11	119.8
C1—C2—C3	122.97 (14)	C12—C11—H11	119.8
C1—C2—C7	118.56 (14)	C13—C12—C11	120.60 (17)
C3—C2—C7	118.46 (14)	C13—C12—H12	119.7
C4—C3—C2	120.66 (16)	C11—C12—H12	119.7
C4—C3—H3	119.7	C12—C13—C14	121.09 (16)
C2—C3—H3	119.7	C12—C13—H13	119.5
C3—C4—C5	120.90 (17)	C14—C13—H13	119.5
C3—C4—H4	119.6	C1—C14—C13	122.97 (15)
C5—C4—H4	119.6	C1—C14—C9	118.88 (14)
C6—C5—C4	120.27 (16)	C13—C14—C9	118.12 (15)
C6—C5—H5	119.9	O1—C15—O2	124.50 (15)
C4—C5—H5	119.9	O1—C15—C1	124.58 (15)
C5—C6—C7	121.11 (16)	O2—C15—C1	110.92 (14)
C5—C6—H6	119.4	O2—C16—C17	108.92 (16)
C7—C6—H6	119.4	O2—C16—H16A	109.9
C8—C7—C6	121.98 (15)	C17—C16—H16A	109.9
C8—C7—C2	119.44 (14)	O2—C16—H16B	109.9
C6—C7—C2	118.58 (15)	C17—C16—H16B	109.9
C9—C8—C7	121.98 (15)	H16A—C16—H16B	108.3
C9—C8—H8	119.0	C16—C17—H17A	109.5
C7—C8—H8	119.0	C16—C17—H17B	109.5
C8—C9—C10	121.96 (15)	H17A—C17—H17B	109.5
C8—C9—C14	119.34 (15)	C16—C17—H17C	109.5
C10—C9—C14	118.69 (15)	H17A—C17—H17C	109.5
C11—C10—C9	121.11 (16)	H17B—C17—H17C	109.5

C14—C1—C2—C3	177.19 (15)	C9—C10—C11—C12	0.6 (3)
C15—C1—C2—C3	−1.3 (2)	C10—C11—C12—C13	−0.2 (3)
C14—C1—C2—C7	−1.8 (2)	C11—C12—C13—C14	−0.3 (3)
C15—C1—C2—C7	179.65 (14)	C2—C1—C14—C13	−179.90 (15)
C1—C2—C3—C4	−178.95 (16)	C15—C1—C14—C13	−1.4 (2)
C7—C2—C3—C4	0.1 (2)	C2—C1—C14—C9	2.0 (2)
C2—C3—C4—C5	−1.0 (3)	C15—C1—C14—C9	−179.43 (15)
C3—C4—C5—C6	0.7 (3)	C12—C13—C14—C1	−177.67 (17)
C4—C5—C6—C7	0.6 (3)	C12—C13—C14—C9	0.4 (3)
C5—C6—C7—C8	178.35 (17)	C8—C9—C14—C1	−0.8 (2)
C5—C6—C7—C2	−1.5 (3)	C10—C9—C14—C1	178.09 (15)
C1—C2—C7—C8	0.3 (2)	C8—C9—C14—C13	−178.94 (15)
C3—C2—C7—C8	−178.70 (16)	C10—C9—C14—C13	−0.1 (2)
C1—C2—C7—C6	−179.79 (16)	C16—O2—C15—O1	−4.4 (3)
C3—C2—C7—C6	1.2 (2)	C16—O2—C15—C1	176.17 (15)
C6—C7—C8—C9	−178.99 (16)	C14—C1—C15—O1	−74.0 (2)
C2—C7—C8—C9	0.9 (3)	C2—C1—C15—O1	104.6 (2)
C7—C8—C9—C10	−179.49 (16)	C14—C1—C15—O2	105.43 (17)
C7—C8—C9—C14	−0.7 (3)	C2—C1—C15—O2	−76.00 (19)
C8—C9—C10—C11	178.42 (18)	C15—O2—C16—C17	−108.52 (18)
C14—C9—C10—C11	−0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.93	2.53	3.302 (2)	140

Symmetry code: (i) −x, −y+2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₄O₂
M_r	250.28
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	153
a, b, c (Å)	8.5431 (6), 10.2137 (7), 14.5426 (11)
V (Å³)	1268.94 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15373, 2020, 1600
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.717

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.085, 1.04
No. of reflections	2020
No. of parameters	174
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.93	2.53	3.302 (2)	140.4

Symmetry code: (i) −x, −y+2, z+1/2.

Acknowledgements

Financial support from the German Federal Ministry of Economics and Technology (BMWi) under grant No. 16IN0218 `ChemoChips' is gratefully acknowledged. L. M. S. F. Bendrath thanks Dr T. Gruber for supervision of her practical work.

References

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Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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