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Acta Cryst. (2007). E63, o3972-o3973    [ doi:10.1107/S1600536807042663 ]

Ethyl (9-oxo-9,10-dihydroacridin-10-yl)acetate

K. Krzyminski, A. Sikorski and J. Blazejowski

Abstract top

In the crystal structure of the title compound, C17H15NO3, molecules related by a center of symmetry are arranged in pairs that are stabilized via [pi]-[pi] interactions between the acridinone units. Adjacent pairs, with the acridinone rings arranged in a herringbone pattern, are linked through a network of [pi]-[pi] and C-H...O interactions.

Comment top

9-Acridinones strongly fluoresce in visible region (Boużyk et al., 2003) which brings about that they can serve as emitting fragments of fluorogenic indicators or labels. 9-Acridinone derivatives attached through a spacer to macromolcules have been applied among others in fluorometric assay of peptides (Faller et al., 1997) and avidin or streptavidin (Agiamarnioti et al., 2006). A highly sensitive assay for antibody catalysis has also been demonstrated by using a number of 9-acridinone labelled compounds (Reymond et al., 1996). Our investigations have been focused on search for 9-acridinone indicators exhibiting moderate polarity and ability to be transported through cell membranes and accumulated selectivity in various tissues. Ethyl 9-(2-oxoacridin-10(9H)-yl)acetate, (I), is the ethyl ester of (9-oxoacridin-10(9H)-yl) acetic acid whose crystal structure was determined in the past (Dobrzynska & Turowska-Tyrk, 1997).

The parameters characterizing the geometry (Figure 1) of the title compound (Table 1) are typical for 9-acridinones (Dobrzynska & Turowska-Tyrk, 1997; Dzyabchenko et al., 1980; Zavodnik et al., 1979; Zavodnik et al., 1981).

In the monoclinic crystal structure of (I), molecules related by a centre of symmetry are arranged in pairs stabilized via π-π interactions between acridinone units (Table 3, Figure 2). With average deviation from planarity of 0.030 Å, acridinone ring systems (given by C1—C9, N10, C11—C14 atoms) are parallel in pairs, whereas those in adjacent pairs are inclined to each other either at 0.0 (1)° (parallely oriented pairs) or 85.8 (1)° (perpendicularly oriented pairs). Parallely oriented pairs are linked by π-π interactions (Table 3, Figure 2), while perpendicularly oriented pairs - through the network of C—H···O interactions involving acridinone and carbonyl O atoms (Table 2, Figure 2). The view along the c axis demonstrates the arrangement of the acridinone ring in a herringbone pattern.

Related literature top

For general background, see: Agiamarnioti et al. (2006); Boużyk et al. (2003); Faller et al. (1997); Reymond et al. (1996). For related structures, see: Dobrzynska & Turowska-Tyrk (1997); Dzyabchenko et al. (1980); Zavodnik et al. (1979, 1981).

Experimental top

The title compound was synthesized by treating 9(10H)-acridinone with five molar excess of ethyl iodoacetate, both dissolved in dry dimethylsulfoxide, in the presence of anhydrous potassium carbonate (323 K, 8 h). The reaction mixture was poured into diluted hydrochloric acid, and the crude product was isolated by filtration and purified by gravitational column chromatography (SiO2, chloroform/ethanol, 10:1 v/v). Yellow crystals of (I) suitable for X-ray investigations were grown from acetone [m.p. = 455–457 K; elemental analysis (% calculated/found): C 72.58/72.36, H 5.37/5.26, N 4.98/4.96].

Refinement top

Methyl H atoms were placed in calculated positions with C—H = 0.98 Å and torsion angle was refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 (aromatic) and 0.99 Å (methylene), and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radius.
[Figure 2] Fig. 2. The arrangement of the molecules of (I) in the crystal structure viewed approximately along the c axis. The C—H···O interactions are represented by dashed lines and π-π interactions by dotted lines. H atoms not involved in C—H···O interactions have been omitted. [Symmetry codes: (i) 3/2 − x, y − 1/2, 1/2 − z; (ii) x − 1/2, 1/2 − y, z − 1/2; (iii) 1 − x, −y, 1 − z; (iv) 1 − x, 1 − y, 1 − z].
Ethyl (9-oxo-9,10-dihydroacridin-10-yl)acetate top
Crystal data top
C17H15NO3F000 = 592
Mr = 281.30Dx = 1.350 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2420 reflections
a = 11.3232 (3) Åθ = 3.3–25.0º
b = 10.3380 (2) ŵ = 0.09 mm−1
c = 11.8925 (3) ÅT = 100 (2) K
β = 96.069 (2)ºBlock, yellow
V = 1384.33 (6) Å30.26 × 0.26 × 0.12 mm
Z = 4
Data collection top
Oxford Diffraction GEMINI R ULTRA
diffractometer		2426 independent reflections
Radiation source: fine-focus sealed tube1776 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 100(2) Kθmax = 25.0º
ω scansθmin = 3.3º
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		h = −12→13
Tmin = 0.978, Tmax = 0.991k = −12→12
8822 measured reflectionsl = −14→11
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.066P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.095(Δ/σ)max < 0.001
S = 0.98Δρmax = 0.19 e Å−3
2426 reflectionsΔρmin = −0.20 e Å−3
191 parametersExtinction correction: SHELXL97 (Sheldrick, 1997)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: none
Secondary atom site location: difference Fourier map
Crystal data top
C17H15NO3V = 1384.33 (6) Å3
Mr = 281.30Z = 4
Monoclinic, P21/nMo Kα
a = 11.3232 (3) ŵ = 0.09 mm−1
b = 10.3380 (2) ÅT = 100 (2) K
c = 11.8925 (3) Å0.26 × 0.26 × 0.12 mm
β = 96.069 (2)º
Data collection top
Oxford Diffraction GEMINI R ULTRA
diffractometer		2426 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		1776 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.991Rint = 0.022
8822 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037191 parameters
wR(F2) = 0.095H-atom parameters constrained
S = 0.98Δρmax = 0.19 e Å−3
2426 reflectionsΔρmin = −0.20 e Å−3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.74768 (11)0.07698 (13)0.59379 (11)0.0255 (3)
H10.78520.09560.66730.031*
C20.79552 (12)−0.01492 (14)0.53008 (12)0.0301 (4)
H20.8643−0.06140.55940.036*
C30.74185 (12)−0.03963 (14)0.42115 (12)0.0318 (4)
H30.7762−0.10130.37510.038*
C40.64007 (12)0.02402 (13)0.37971 (12)0.0272 (3)
H40.60490.00570.30530.033*
C50.33185 (11)0.34410 (12)0.42677 (11)0.0235 (3)
H50.29080.32070.35590.028*
C60.29030 (11)0.44419 (13)0.48748 (11)0.0263 (3)
H60.22100.48940.45760.032*
C70.34785 (12)0.48082 (13)0.59227 (12)0.0267 (3)
H70.31880.55080.63320.032*
C80.44674 (11)0.41402 (12)0.63490 (11)0.0238 (3)
H80.48590.43770.70660.029*
C90.59786 (11)0.24433 (12)0.62432 (11)0.0220 (3)
N100.48050 (9)0.17667 (10)0.40685 (8)0.0211 (3)
C110.64392 (11)0.14521 (12)0.55352 (11)0.0209 (3)
C120.58718 (11)0.11590 (12)0.44574 (11)0.0213 (3)
C130.49175 (11)0.31132 (12)0.57522 (10)0.0202 (3)
C140.43467 (10)0.27592 (12)0.46854 (10)0.0194 (3)
O150.64646 (8)0.27032 (9)0.72029 (7)0.0296 (3)
C160.42514 (12)0.14381 (13)0.29409 (10)0.0226 (3)
H16A0.33990.16720.28810.027*
H16B0.43080.04930.28240.027*
C170.48365 (11)0.21345 (12)0.20307 (11)0.0224 (3)
O180.44395 (8)0.16691 (8)0.10116 (7)0.0251 (3)
C190.49230 (12)0.22930 (14)0.00575 (11)0.0269 (3)
H19B0.57810.20990.00730.032*
H19A0.48240.32430.01000.032*
C200.42657 (16)0.17831 (15)−0.10081 (12)0.0428 (4)
H20C0.43280.0838−0.10200.064*
H20B0.46100.2145−0.16620.064*
H20A0.34280.2033−0.10400.064*
O210.55459 (8)0.29938 (9)0.21883 (8)0.0341 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0215 (7)0.0294 (8)0.0253 (7)−0.0023 (6)0.0007 (6)0.0009 (6)
C20.0221 (8)0.0314 (8)0.0365 (9)0.0054 (6)0.0022 (7)0.0000 (7)
C30.0308 (8)0.0309 (8)0.0348 (9)0.0037 (6)0.0087 (7)−0.0051 (7)
C40.0287 (8)0.0291 (8)0.0238 (8)−0.0002 (6)0.0029 (6)−0.0043 (6)
C50.0232 (7)0.0267 (7)0.0194 (7)−0.0019 (6)−0.0028 (6)0.0018 (6)
C60.0210 (7)0.0275 (8)0.0295 (8)0.0018 (6)−0.0015 (6)0.0029 (6)
C70.0260 (8)0.0248 (7)0.0291 (8)0.0027 (6)0.0018 (6)−0.0043 (6)
C80.0244 (7)0.0267 (7)0.0200 (7)−0.0025 (6)0.0007 (6)−0.0026 (6)
C90.0207 (7)0.0264 (7)0.0186 (7)−0.0029 (6)0.0007 (6)0.0013 (6)
N100.0207 (6)0.0259 (6)0.0160 (6)0.0000 (5)−0.0006 (5)−0.0019 (5)
C110.0183 (7)0.0225 (7)0.0219 (7)−0.0022 (5)0.0021 (6)0.0015 (6)
C120.0206 (7)0.0219 (7)0.0216 (7)−0.0021 (5)0.0034 (6)0.0018 (6)
C130.0182 (7)0.0226 (7)0.0199 (7)−0.0031 (5)0.0018 (5)0.0005 (6)
C140.0195 (7)0.0204 (7)0.0183 (7)−0.0041 (6)0.0020 (6)0.0003 (5)
O150.0279 (5)0.0393 (6)0.0198 (5)0.0057 (4)−0.0055 (4)−0.0047 (4)
C160.0236 (7)0.0259 (7)0.0179 (7)−0.0035 (6)0.0005 (6)−0.0040 (6)
C170.0207 (7)0.0242 (7)0.0216 (7)−0.0008 (6)−0.0005 (6)−0.0033 (6)
O180.0305 (5)0.0283 (5)0.0166 (5)−0.0085 (4)0.0027 (4)−0.0011 (4)
C190.0308 (8)0.0290 (7)0.0221 (8)−0.0046 (6)0.0082 (6)0.0010 (6)
C200.0590 (11)0.0476 (9)0.0222 (8)−0.0208 (8)0.0055 (8)0.0000 (7)
O210.0375 (6)0.0378 (6)0.0270 (6)−0.0165 (5)0.0032 (5)−0.0067 (5)
Geometric parameters (Å, °) top
C1—C21.363 (2)C9—C111.4574 (18)
C1—C111.4100 (17)C9—O151.2428 (14)
C1—H10.9500N10—C121.3962 (16)
C2—C31.3951 (19)N10—C141.3932 (16)
C2—H20.9500N10—C161.4591 (15)
C3—C41.3725 (19)C11—C121.4048 (17)
C3—H30.9500C13—C141.4099 (16)
C4—C121.4061 (19)C16—C171.5102 (19)
C4—H40.9500C16—H16A0.9900
C5—C61.3731 (19)C16—H16B0.9900
C5—C141.4060 (17)C17—O181.3369 (15)
C5—H50.9500C17—O211.1990 (15)
C6—C71.3962 (18)O18—C191.4610 (16)
C6—H60.9500C19—C201.4961 (18)
C7—C81.3666 (18)C19—H19B0.9900
C7—H70.9500C19—H19A0.9900
C8—C131.4026 (18)C20—H20C0.9800
C8—H80.9500C20—H20B0.9800
C9—C131.4546 (17)C20—H20A0.9800
C2—C1—C11121.73 (12)C1—C11—C9119.45 (11)
C2—C1—H1119.1N10—C12—C11120.09 (12)
C11—C1—H1119.1N10—C12—C4121.58 (11)
C1—C2—C3118.96 (12)C11—C12—C4118.33 (11)
C1—C2—H2120.5C8—C13—C14119.69 (11)
C3—C2—H2120.5C8—C13—C9119.09 (11)
C4—C3—C2120.83 (14)C14—C13—C9121.22 (12)
C4—C3—H3119.6N10—C14—C5121.58 (11)
C2—C3—H3119.6N10—C14—C13120.28 (11)
C3—C4—C12120.96 (12)C5—C14—C13118.14 (12)
C3—C4—H4119.5N10—C16—H16A109.3
C12—C4—H4119.5C17—C16—H16A109.3
C6—C5—C14120.59 (12)N10—C16—H16B109.3
C6—C5—H5119.7C17—C16—H16B109.3
C14—C5—H5119.7H16B—C16—H16B107.9
C5—C6—C7121.35 (12)C16—C17—O18110.32 (10)
C5—C6—H6119.3C16—C17—O21125.35 (12)
C7—C6—H6119.3C17—O18—C19115.31 (9)
C8—C7—C6118.74 (13)O18—C17—O21124.32 (12)
C8—C7—H7120.6O18—C19—C20107.97 (11)
C6—C7—H7120.6O18—C19—H19B110.1
C7—C8—C13121.47 (11)C20—C19—H19B110.1
C7—C8—H8119.3O18—C19—H19A110.1
C13—C8—H8119.3C20—C19—H19A110.1
O15—C9—C13122.17 (12)H19B—C19—H19A108.4
O15—C9—C11122.13 (11)C19—C20—H20C109.5
N10—C16—C17111.68 (10)C19—C20—H20B109.5
C11—C9—C13115.70 (11)H20C—C20—H20B109.5
C12—N10—C14120.95 (10)C19—C20—H20A109.5
C14—N10—C16120.51 (10)H20C—C20—H20A109.5
C12—C11—C1119.10 (12)H20B—C20—H20A109.5
C12—C11—C9121.45 (11)
C11—C1—C2—C31.6 (2)C9—C11—C12—C4176.68 (12)
C1—C2—C3—C4−2.3 (2)C3—C4—C12—N10−176.76 (12)
C2—C3—C4—C120.1 (2)C3—C4—C12—C112.7 (2)
C14—C5—C6—C7−0.4 (2)C7—C8—C13—C140.3 (2)
C5—C6—C7—C8−0.7 (2)C7—C8—C13—C9179.52 (12)
C6—C7—C8—C130.7 (2)O15—C9—C13—C84.02 (19)
C2—C1—C11—C121.2 (2)C11—C9—C13—C8−175.67 (11)
C2—C1—C11—C9−178.80 (12)O15—C9—C13—C14−176.81 (12)
O15—C9—C11—C12179.25 (12)C12—N10—C14—C5175.47 (12)
C13—C9—C11—C12−1.06 (18)C16—N10—C14—C52.45 (18)
O15—C9—C11—C1−0.74 (19)C16—N10—C14—C13−177.02 (11)
C13—C9—C11—C1178.95 (11)C6—C5—C14—N10−178.01 (12)
C14—N10—C12—C116.44 (18)C6—C5—C14—C131.47 (19)
C16—N10—C12—C11179.62 (11)C8—C13—C14—N10178.06 (11)
C14—N10—C12—C4−174.07 (11)C9—C13—C14—N10−1.10 (18)
C16—N10—C12—C4−0.88 (18)C8—C13—C14—C5−1.43 (18)
C1—C11—C12—C4−3.34 (19)C9—C13—C14—C5179.41 (11)
N10—C16—C17—O18170.44 (10)C14—N10—C16—C1793.93 (13)
N10—C16—C17—O21−10.40 (19)C12—N10—C16—C17−79.29 (14)
C11—C9—C13—C143.50 (18)O21—C17—O18—C19−0.61 (18)
C12—N10—C14—C13−4.00 (18)C16—C17—O18—C19178.56 (10)
C1—C11—C12—N10176.17 (11)C17—O18—C19—C20−172.36 (12)
C9—C11—C12—N10−3.82 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O21i0.952.533.4155 (17)154
C5—H5···O15ii0.952.373.2781 (15)161
C16—H16A···O15ii0.992.343.3061 (16)164
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2.
Selected geometric parameters (Å, °) top
C9—C111.4574 (18)C17—O181.3369 (15)
C9—O151.2428 (14)C17—O211.1990 (15)
N10—C161.4591 (15)O18—C191.4610 (16)
N10—C16—C17111.68 (10)C16—C17—O21125.35 (12)
C11—C9—C13115.70 (11)C17—O18—C19115.31 (9)
C12—N10—C14120.95 (10)O18—C17—O21124.32 (12)
C14—N10—C16120.51 (10)O18—C19—C20107.97 (11)
C16—C17—O18110.32 (10)
C1—C11—C12—C4−3.34 (19)C11—C9—C13—C143.50 (18)
N10—C16—C17—O18170.44 (10)C12—N10—C14—C13−4.00 (18)
N10—C16—C17—O21−10.40 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O21i0.952.533.4155 (17)154
C5—H5···O15ii0.952.373.2781 (15)161
C16—H16A···O15ii0.992.343.3061 (16)164
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2.
π–π interactions (Å,°) top
CgICgJCg···CgDihedral angleInterplanar distanceOffset
12iii3.780 (1)3.13.4921.361 (3)
21iii3.780 (1)3.13.4171.422 (3)
33iv3.660 (1)0.03.5301.853 (3)
Symmetry codes: (iii) 1 − x, −y, 1 − z; (iv) 1 − x, 1 − y, 1 − z.

Notes: Cg1 is the centroid of ring C9/C11/C12/N10/C14/C13, Cg2 is the centroid of ring C1–C4/C12/C11 and Cg3 is the centroid of ring C5–C8/C13/C14. Cg···Cg is the distance between ring centroids. The dihedral angle is that between the planes of rings CgI and CgJ. The interplanar distance is the perpendicular distance of CgI from ring J. The offset is computed as the third side of the right-angled triangle involving the Cg···Cg distance.
Acknowledgements top

This study was financed from the State Funds for Scientific Research (grant BW/8000–5–0047–7). The authors thank Oxford Diffraction Ltd, Abingdon, Oxfordshire, England, and Dr N. Brooks from this company for the data collection and for providing access to crystallographic experimental facilities.

references
References top

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