organic compounds
9-(4-Methylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate
aFaculty of Chemistry, University of Gdańsk, J. Sobieskiego 18, 80-952 Gdańsk, Poland
*Correspondence e-mail: bla@chem.univ.gda.pl
In the 22H18NO2+·CF3SO3−, adjacent cations are linked through C—H⋯π and π–π interactions, and the cations and anions are connected by C—H⋯O and C—F⋯π interactions. The acridine and benzene ring systems are oriented at a dihedral angle of 3.0 (1)°. The carboxyl group is twisted at an angle of 83.1 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel or inclined at an angle of 75.2 (1)° in the crystal structure.
of the title compound, CRelated literature
For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009); Rak et al. (1999); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2006); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006); Takahashi et al. (2001). For the synthesis, see: Sato (1996); Sikorski et al. (2006); Trzybiński et al. (2010).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell CrysAlis RED; data reduction: CrysAlis RED; 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: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536810016302/ng2760sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016302/ng2760Isup2.hkl
The compound was synthesized as described elsewhere (Sikorski et al., 2006; Trzybiński et al., 2010), i.e., 9-(chlorocarbonyl)acridine obtained by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride was esterified with 4-methylphenol in anhydrous dichloromethane in the presence of N,N-diethylethanamine and a catalytic amount of N,N-dimethyl-4-pyridinamine (room temperature, 15h) (Sato, 1996). The product – 4-methylphenyl acridine-9-carboxylate, purified chromatographically (SiO2, cyclohexane/ethyl acetate, 3/2 v/v) – was quaternarized with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane. The crude 9-(4-methylphenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with 25 v/v excess of diethyl ether. Light-orange crystals suitable for X-ray investigations were grown from absolute ethanol solution (m.p. 445 - 447 K).
H atoms were positioned geometrically, with C—H = 0.93 Å and 0.96 Å for the aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.2 for the aromatic and x = 1.5 for the methyl H atoms.
9-(Phenoxycarbonyl)-10-methylacridinium salts appear to be convenient chemiluminescent indicators or the chemiluminogenic fragments of chemiluminescent labels (Zomer & Jacquemijns, 2001), which are widely applied in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Roda et al., 2003; Brown et al., 2009). Oxidation of the cations of these salts with hydrogen peroxide in alkaline media is accompanied by the removal of the phenoxycarbonyl fragment and the conversion of the remaining part of the molecule to electronically excited, light emitting 10-methyl-9-acridinone (Rak et al., 1999; Zomer & Jacquemijns, 2001). The efficiency of
– crucial for analytical applications – is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). This prompted us to undertake investigations on derivatives substituted in this fragment. Here we present the structure of 9-(4-methylphenoxy)carbonyl-10-methylacridinium trifluoromethanesulfonate, a structural isomer of the 2-methyl substituted salt, whose structure has already been refined (Sikorski et al., 2006).In the cation of the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the acridinium moiety are typical of acridine-based derivatives (Sikorski et al., 2006; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0386 (3) Å and 0.0017 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 3.0 (1)°. The carboxyl group is twisted at an angle of 83.1 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (remain at an angle of 0.0 (1)°) or inclined at an angle of 75.2 (1)° in the lattice.
In the π (Table 1, Fig. 2) and π–π (involving acridine and phenyl moieties) (Table 3, Fig. 2) interactions, and cations and anions are connected by multidirectional C–H···O (Table 1, Figs. 1 and 2) and C–F···π (Table 2, Fig. 2) interactions. The C–H···O interactions are of the hydrogen bond type (Bianchi et al. 2004; Novoa et al., 2006). The C–H···π interactions should be of an attractive nature (Takahashi et al., 2001), like the C–F···π (Dorn et al., 2005) and π–π (Hunter et al., 2001) interactions. The is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.
the adjacent cations are linked through C–H···For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Brown et al. (2009); Rak et al. (1999); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2006); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006); Takahashi et al. (2001). For the synthesis, see: Sato (1996); Sikorski et al. (2006); Trzybiński et al. (2010).
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell
CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED; 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radius. Cg1, Cg2, Cg3 and Cg4 denote the ring centroids. The C–H···O hydrogen bonds are represented by dashed lines. | |
Fig. 2. The arrangement of the ions in the crystal structure. The C–H···O interactions are represented by dashed lines, the C–H···π, C–F···π and π–π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) –x + 3/2, y + 1/2, –z + 1/2; (ii) –x + 2, –y + 1, –z + 1; (iii) x – 1, y, z; (iv) –x + 1, –y + 1, –z + 1; (v) –x + 1, –y, –z + 1.] |
C22H18NO2+·CF3O3S− | F(000) = 984 |
Mr = 477.45 | Dx = 1.442 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3355 reflections |
a = 13.2686 (6) Å | θ = 3.1–29.2° |
b = 8.4788 (4) Å | µ = 0.21 mm−1 |
c = 20.4078 (10) Å | T = 295 K |
β = 106.749 (5)° | Plate, light-orange |
V = 2198.51 (19) Å3 | 0.50 × 0.40 × 0.10 mm |
Z = 4 |
Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer | 3892 independent reflections |
Radiation source: enhanced (Mo) X-Ray Source | 2096 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 10.4002 pixels mm-1 | θmax = 25.1°, θmin = 3.1° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | k = −10→10 |
Tmin = 0.869, Tmax = 1.000 | l = −24→24 |
12172 measured reflections |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0678P)2] where P = (Fo2 + 2Fc2)/3 |
3892 reflections | (Δ/σ)max < 0.001 |
299 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C22H18NO2+·CF3O3S− | V = 2198.51 (19) Å3 |
Mr = 477.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.2686 (6) Å | µ = 0.21 mm−1 |
b = 8.4788 (4) Å | T = 295 K |
c = 20.4078 (10) Å | 0.50 × 0.40 × 0.10 mm |
β = 106.749 (5)° |
Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer | 3892 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008) | 2096 reflections with I > 2σ(I) |
Tmin = 0.869, Tmax = 1.000 | Rint = 0.061 |
12172 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.23 e Å−3 |
3892 reflections | Δρmin = −0.19 e Å−3 |
299 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3367 (3) | 0.4502 (4) | 0.3326 (2) | 0.0699 (10) | |
H1 | 0.2898 | 0.4002 | 0.3519 | 0.084* | |
C2 | 0.2997 (3) | 0.5409 (5) | 0.2766 (2) | 0.0918 (13) | |
H2 | 0.2276 | 0.5502 | 0.2563 | 0.110* | |
C3 | 0.3705 (3) | 0.6211 (5) | 0.2491 (2) | 0.0957 (14) | |
H3 | 0.3441 | 0.6854 | 0.2111 | 0.115* | |
C4 | 0.4760 (3) | 0.6083 (4) | 0.2759 (2) | 0.0691 (10) | |
H4 | 0.5208 | 0.6634 | 0.2565 | 0.083* | |
C5 | 0.7739 (3) | 0.3924 (4) | 0.44967 (19) | 0.0631 (9) | |
H5 | 0.8203 | 0.4433 | 0.4302 | 0.076* | |
C6 | 0.8115 (3) | 0.3064 (5) | 0.5083 (2) | 0.0735 (10) | |
H6 | 0.8838 | 0.3013 | 0.5287 | 0.088* | |
C7 | 0.7440 (3) | 0.2253 (5) | 0.5386 (2) | 0.0766 (11) | |
H7 | 0.7713 | 0.1667 | 0.5783 | 0.092* | |
C8 | 0.6389 (3) | 0.2334 (4) | 0.50934 (18) | 0.0639 (10) | |
H8 | 0.5944 | 0.1786 | 0.5291 | 0.077* | |
C9 | 0.4876 (3) | 0.3337 (4) | 0.41922 (16) | 0.0479 (8) | |
N10 | 0.62352 (19) | 0.4910 (3) | 0.36094 (13) | 0.0486 (7) | |
C11 | 0.4461 (2) | 0.4303 (4) | 0.36217 (16) | 0.0498 (8) | |
C12 | 0.5177 (2) | 0.5109 (4) | 0.33342 (16) | 0.0495 (8) | |
C13 | 0.5948 (3) | 0.3229 (4) | 0.44951 (16) | 0.0507 (8) | |
C14 | 0.6651 (2) | 0.4037 (4) | 0.41908 (16) | 0.0473 (8) | |
C15 | 0.4137 (3) | 0.2312 (4) | 0.44360 (17) | 0.0548 (9) | |
O16 | 0.38896 (18) | 0.2932 (3) | 0.49667 (12) | 0.0648 (7) | |
O17 | 0.3828 (2) | 0.1080 (3) | 0.41764 (13) | 0.0858 (9) | |
C18 | 0.3185 (3) | 0.2065 (4) | 0.52390 (16) | 0.0500 (8) | |
C19 | 0.3597 (3) | 0.1129 (4) | 0.57992 (17) | 0.0609 (9) | |
H19 | 0.4321 | 0.0997 | 0.5978 | 0.073* | |
C20 | 0.2903 (3) | 0.0381 (4) | 0.60930 (17) | 0.0652 (10) | |
H20 | 0.3170 | −0.0262 | 0.6473 | 0.078* | |
C21 | 0.1839 (3) | 0.0565 (4) | 0.58395 (19) | 0.0647 (10) | |
C22 | 0.1461 (3) | 0.1515 (5) | 0.52795 (19) | 0.0671 (10) | |
H22 | 0.0739 | 0.1655 | 0.5102 | 0.081* | |
C23 | 0.2132 (3) | 0.2273 (4) | 0.49707 (17) | 0.0593 (9) | |
H23 | 0.1866 | 0.2908 | 0.4589 | 0.071* | |
C24 | 0.1088 (4) | −0.0241 (5) | 0.6176 (2) | 0.1041 (15) | |
H24A | 0.0428 | 0.0309 | 0.6055 | 0.156* | |
H24B | 0.1387 | −0.0225 | 0.6664 | 0.156* | |
H24C | 0.0978 | −0.1313 | 0.6021 | 0.156* | |
C25 | 0.6972 (3) | 0.5623 (4) | 0.32692 (17) | 0.0655 (10) | |
H25A | 0.7583 | 0.4964 | 0.3343 | 0.098* | |
H25B | 0.7180 | 0.6650 | 0.3458 | 0.098* | |
H25C | 0.6632 | 0.5715 | 0.2787 | 0.098* | |
S26 | 0.98783 (7) | 0.47984 (11) | 0.33273 (4) | 0.0560 (3) | |
O27 | 1.09157 (18) | 0.4193 (3) | 0.34606 (12) | 0.0801 (8) | |
O28 | 0.96339 (18) | 0.5485 (3) | 0.39004 (12) | 0.0844 (8) | |
O29 | 0.90554 (18) | 0.3856 (3) | 0.28984 (12) | 0.0688 (7) | |
C30 | 0.9911 (3) | 0.6484 (5) | 0.2789 (2) | 0.0737 (11) | |
F31 | 1.0614 (2) | 0.7536 (3) | 0.31098 (15) | 0.1247 (10) | |
F32 | 1.0156 (2) | 0.6073 (4) | 0.22295 (13) | 0.1123 (9) | |
F33 | 0.8988 (2) | 0.7204 (3) | 0.25876 (13) | 0.1117 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.057 (2) | 0.061 (2) | 0.098 (3) | −0.003 (2) | 0.033 (2) | 0.014 (2) |
C2 | 0.050 (2) | 0.096 (3) | 0.131 (4) | 0.012 (2) | 0.029 (2) | 0.033 (3) |
C3 | 0.078 (3) | 0.090 (3) | 0.117 (3) | 0.012 (3) | 0.027 (3) | 0.046 (3) |
C4 | 0.056 (2) | 0.060 (2) | 0.098 (3) | −0.0012 (19) | 0.032 (2) | 0.019 (2) |
C5 | 0.060 (2) | 0.052 (2) | 0.079 (3) | −0.0077 (19) | 0.022 (2) | −0.011 (2) |
C6 | 0.061 (2) | 0.063 (3) | 0.085 (3) | −0.001 (2) | 0.003 (2) | −0.010 (2) |
C7 | 0.086 (3) | 0.063 (3) | 0.073 (3) | −0.001 (2) | 0.011 (2) | 0.004 (2) |
C8 | 0.071 (3) | 0.054 (2) | 0.067 (2) | −0.008 (2) | 0.020 (2) | −0.003 (2) |
C9 | 0.058 (2) | 0.0330 (18) | 0.060 (2) | −0.0060 (16) | 0.0285 (18) | −0.0113 (17) |
N10 | 0.0474 (17) | 0.0375 (15) | 0.0676 (17) | −0.0061 (13) | 0.0274 (14) | −0.0070 (14) |
C11 | 0.048 (2) | 0.0370 (18) | 0.071 (2) | −0.0068 (16) | 0.0289 (18) | −0.0049 (18) |
C12 | 0.052 (2) | 0.0331 (19) | 0.067 (2) | −0.0010 (16) | 0.0229 (17) | −0.0037 (17) |
C13 | 0.063 (2) | 0.0320 (18) | 0.060 (2) | −0.0040 (17) | 0.0225 (18) | −0.0059 (16) |
C14 | 0.046 (2) | 0.0351 (18) | 0.063 (2) | −0.0052 (15) | 0.0203 (17) | −0.0105 (17) |
C15 | 0.068 (2) | 0.040 (2) | 0.066 (2) | −0.0062 (18) | 0.0334 (19) | −0.0037 (18) |
O16 | 0.0833 (17) | 0.0462 (14) | 0.0804 (16) | −0.0143 (13) | 0.0485 (14) | −0.0130 (12) |
O17 | 0.122 (2) | 0.0581 (17) | 0.1013 (19) | −0.0380 (16) | 0.0701 (18) | −0.0252 (16) |
C18 | 0.066 (2) | 0.0374 (19) | 0.054 (2) | −0.0074 (18) | 0.0285 (19) | −0.0066 (17) |
C19 | 0.061 (2) | 0.057 (2) | 0.066 (2) | −0.0032 (19) | 0.0198 (19) | −0.008 (2) |
C20 | 0.091 (3) | 0.054 (2) | 0.0529 (19) | −0.004 (2) | 0.024 (2) | 0.0038 (18) |
C21 | 0.074 (3) | 0.068 (3) | 0.060 (2) | −0.014 (2) | 0.032 (2) | −0.014 (2) |
C22 | 0.061 (2) | 0.078 (3) | 0.068 (2) | −0.001 (2) | 0.027 (2) | −0.004 (2) |
C23 | 0.072 (3) | 0.055 (2) | 0.053 (2) | 0.002 (2) | 0.0214 (19) | 0.0023 (17) |
C24 | 0.141 (4) | 0.097 (3) | 0.099 (3) | −0.038 (3) | 0.074 (3) | −0.008 (3) |
C25 | 0.058 (2) | 0.068 (2) | 0.079 (2) | −0.0098 (19) | 0.0331 (19) | −0.0052 (19) |
S26 | 0.0511 (5) | 0.0592 (6) | 0.0605 (5) | 0.0019 (5) | 0.0208 (4) | 0.0024 (5) |
O27 | 0.0581 (15) | 0.0891 (19) | 0.0933 (18) | 0.0225 (14) | 0.0221 (13) | 0.0194 (15) |
O28 | 0.0716 (16) | 0.118 (2) | 0.0732 (16) | −0.0188 (16) | 0.0366 (14) | −0.0244 (15) |
O29 | 0.0627 (15) | 0.0584 (15) | 0.0878 (17) | −0.0099 (12) | 0.0258 (13) | −0.0128 (13) |
C30 | 0.062 (3) | 0.066 (3) | 0.087 (3) | −0.012 (2) | 0.011 (2) | 0.000 (2) |
F31 | 0.122 (2) | 0.0878 (19) | 0.140 (2) | −0.0465 (17) | 0.0005 (17) | 0.0175 (16) |
F32 | 0.114 (2) | 0.147 (2) | 0.0809 (15) | −0.0172 (17) | 0.0356 (14) | 0.0272 (16) |
F33 | 0.0992 (18) | 0.0718 (16) | 0.142 (2) | 0.0200 (15) | −0.0010 (16) | 0.0185 (15) |
C1—C2 | 1.347 (5) | C15—O16 | 1.327 (4) |
C1—C11 | 1.412 (4) | O16—C18 | 1.421 (3) |
C1—H1 | 0.9300 | C18—C23 | 1.357 (4) |
C2—C3 | 1.401 (5) | C18—C19 | 1.370 (4) |
C2—H2 | 0.9300 | C19—C20 | 1.388 (5) |
C3—C4 | 1.352 (5) | C19—H19 | 0.9300 |
C3—H3 | 0.9300 | C20—C21 | 1.366 (5) |
C4—C12 | 1.411 (5) | C20—H20 | 0.9300 |
C4—H4 | 0.9300 | C21—C22 | 1.369 (5) |
C5—C6 | 1.366 (5) | C21—C24 | 1.524 (5) |
C5—C14 | 1.401 (4) | C22—C23 | 1.388 (4) |
C5—H5 | 0.9300 | C22—H22 | 0.9300 |
C6—C7 | 1.406 (5) | C23—H23 | 0.9300 |
C6—H6 | 0.9300 | C24—H24A | 0.9600 |
C7—C8 | 1.351 (5) | C24—H24B | 0.9600 |
C7—H7 | 0.9300 | C24—H24C | 0.9600 |
C8—C13 | 1.413 (4) | C25—H25A | 0.9600 |
C8—H8 | 0.9300 | C25—H25B | 0.9600 |
C9—C13 | 1.381 (4) | C25—H25C | 0.9600 |
C9—C11 | 1.400 (4) | S26—O27 | 1.420 (2) |
C9—C15 | 1.499 (4) | S26—O28 | 1.425 (2) |
N10—C12 | 1.364 (4) | S26—O29 | 1.430 (2) |
N10—C14 | 1.372 (4) | S26—C30 | 1.811 (4) |
N10—C25 | 1.481 (4) | C30—F32 | 1.321 (4) |
C11—C12 | 1.427 (4) | C30—F31 | 1.321 (4) |
C13—C14 | 1.434 (4) | C30—F33 | 1.324 (4) |
C15—O17 | 1.189 (4) | ||
C2—C1—C11 | 120.7 (3) | O16—C15—C9 | 112.4 (3) |
C2—C1—H1 | 119.7 | C15—O16—C18 | 117.3 (2) |
C11—C1—H1 | 119.7 | C23—C18—C19 | 121.9 (3) |
C1—C2—C3 | 119.5 (4) | C23—C18—O16 | 119.4 (3) |
C1—C2—H2 | 120.2 | C19—C18—O16 | 118.5 (3) |
C3—C2—H2 | 120.2 | C18—C19—C20 | 118.1 (3) |
C4—C3—C2 | 122.3 (4) | C18—C19—H19 | 121.0 |
C4—C3—H3 | 118.9 | C20—C19—H19 | 121.0 |
C2—C3—H3 | 118.9 | C21—C20—C19 | 121.8 (3) |
C3—C4—C12 | 119.7 (3) | C21—C20—H20 | 119.1 |
C3—C4—H4 | 120.1 | C19—C20—H20 | 119.1 |
C12—C4—H4 | 120.1 | C20—C21—C22 | 118.2 (3) |
C6—C5—C14 | 119.7 (3) | C20—C21—C24 | 121.1 (4) |
C6—C5—H5 | 120.1 | C22—C21—C24 | 120.7 (4) |
C14—C5—H5 | 120.1 | C21—C22—C23 | 121.5 (3) |
C5—C6—C7 | 121.8 (4) | C21—C22—H22 | 119.2 |
C5—C6—H6 | 119.1 | C23—C22—H22 | 119.2 |
C7—C6—H6 | 119.1 | C18—C23—C22 | 118.5 (3) |
C8—C7—C6 | 119.2 (4) | C18—C23—H23 | 120.7 |
C8—C7—H7 | 120.4 | C22—C23—H23 | 120.7 |
C6—C7—H7 | 120.4 | C21—C24—H24A | 109.5 |
C7—C8—C13 | 121.7 (3) | C21—C24—H24B | 109.5 |
C7—C8—H8 | 119.1 | H24A—C24—H24B | 109.5 |
C13—C8—H8 | 119.1 | C21—C24—H24C | 109.5 |
C13—C9—C11 | 121.2 (3) | H24A—C24—H24C | 109.5 |
C13—C9—C15 | 120.1 (3) | H24B—C24—H24C | 109.5 |
C11—C9—C15 | 118.5 (3) | N10—C25—H25A | 109.4 |
C12—N10—C14 | 122.2 (2) | N10—C25—H25B | 109.5 |
C12—N10—C25 | 119.8 (3) | H25A—C25—H25B | 109.5 |
C14—N10—C25 | 118.0 (3) | N10—C25—H25C | 109.6 |
C9—C11—C1 | 122.4 (3) | H25A—C25—H25C | 109.5 |
C9—C11—C12 | 118.2 (3) | H25B—C25—H25C | 109.5 |
C1—C11—C12 | 119.4 (3) | O27—S26—O28 | 115.33 (16) |
N10—C12—C4 | 121.7 (3) | O27—S26—O29 | 116.23 (16) |
N10—C12—C11 | 120.0 (3) | O28—S26—O29 | 114.60 (14) |
C4—C12—C11 | 118.3 (3) | O27—S26—C30 | 102.13 (17) |
C9—C13—C8 | 122.6 (3) | O28—S26—C30 | 103.11 (19) |
C9—C13—C14 | 119.3 (3) | O29—S26—C30 | 102.54 (16) |
C8—C13—C14 | 118.2 (3) | F32—C30—F31 | 107.0 (3) |
N10—C14—C5 | 121.9 (3) | F32—C30—F33 | 106.9 (3) |
N10—C14—C13 | 118.9 (3) | F31—C30—F33 | 107.5 (3) |
C5—C14—C13 | 119.3 (3) | F32—C30—S26 | 111.8 (3) |
O17—C15—O16 | 125.2 (3) | F31—C30—S26 | 111.7 (3) |
O17—C15—C9 | 122.4 (3) | F33—C30—S26 | 111.7 (3) |
C11—C1—C2—C3 | −2.5 (6) | C6—C5—C14—C13 | −0.7 (5) |
C1—C2—C3—C4 | 1.5 (7) | C9—C13—C14—N10 | 0.7 (4) |
C2—C3—C4—C12 | 0.2 (6) | C8—C13—C14—N10 | 180.0 (3) |
C14—C5—C6—C7 | 1.3 (5) | C9—C13—C14—C5 | −179.8 (3) |
C5—C6—C7—C8 | −0.5 (5) | C8—C13—C14—C5 | −0.5 (4) |
C6—C7—C8—C13 | −0.8 (5) | C13—C9—C15—O17 | −94.0 (4) |
C13—C9—C11—C1 | −176.4 (3) | C11—C9—C15—O17 | 81.1 (4) |
C15—C9—C11—C1 | 8.5 (4) | C13—C9—C15—O16 | 85.3 (3) |
C13—C9—C11—C12 | 3.6 (4) | C11—C9—C15—O16 | −99.6 (3) |
C15—C9—C11—C12 | −171.5 (3) | O17—C15—O16—C18 | −1.1 (5) |
C2—C1—C11—C9 | −178.2 (3) | C9—C15—O16—C18 | 179.6 (3) |
C2—C1—C11—C12 | 1.8 (5) | C15—O16—C18—C23 | −87.3 (4) |
C14—N10—C12—C4 | 176.3 (3) | C15—O16—C18—C19 | 97.4 (3) |
C25—N10—C12—C4 | −5.0 (4) | C23—C18—C19—C20 | 0.0 (5) |
C14—N10—C12—C11 | −4.6 (4) | O16—C18—C19—C20 | 175.2 (3) |
C25—N10—C12—C11 | 174.0 (3) | C18—C19—C20—C21 | −0.3 (5) |
C3—C4—C12—N10 | 178.1 (3) | C19—C20—C21—C22 | 0.1 (5) |
C3—C4—C12—C11 | −0.9 (5) | C19—C20—C21—C24 | −178.9 (3) |
C9—C11—C12—N10 | 0.9 (4) | C20—C21—C22—C23 | 0.3 (5) |
C1—C11—C12—N10 | −179.1 (3) | C24—C21—C22—C23 | 179.3 (3) |
C9—C11—C12—C4 | 180.0 (3) | C19—C18—C23—C22 | 0.4 (5) |
C1—C11—C12—C4 | 0.0 (4) | O16—C18—C23—C22 | −174.8 (3) |
C11—C9—C13—C8 | 176.4 (3) | C21—C22—C23—C18 | −0.5 (5) |
C15—C9—C13—C8 | −8.6 (4) | O27—S26—C30—F32 | 58.5 (3) |
C11—C9—C13—C14 | −4.4 (4) | O28—S26—C30—F32 | 178.4 (3) |
C15—C9—C13—C14 | 170.6 (3) | O29—S26—C30—F32 | −62.3 (3) |
C7—C8—C13—C9 | −179.4 (3) | O27—S26—C30—F31 | −61.3 (3) |
C7—C8—C13—C14 | 1.3 (5) | O28—S26—C30—F31 | 58.6 (3) |
C12—N10—C14—C5 | −175.6 (3) | O29—S26—C30—F31 | 177.9 (3) |
C25—N10—C14—C5 | 5.7 (4) | O27—S26—C30—F33 | 178.2 (3) |
C12—N10—C14—C13 | 3.8 (4) | O28—S26—C30—F33 | −61.8 (3) |
C25—N10—C14—C13 | −174.8 (3) | O29—S26—C30—F33 | 57.5 (3) |
C6—C5—C14—N10 | 178.8 (3) |
Cg4 is the centroid of the C18–C23 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O27i | 0.93 | 2.57 | 3.314 (5) | 137 |
C4—H4···O29i | 0.93 | 2.44 | 3.319 (4) | 159 |
C5—H5···O28 | 0.93 | 2.44 | 3.364 (5) | 171 |
C6—H6···O28ii | 0.93 | 2.56 | 3.342 (5) | 142 |
C23—H23···O27iii | 0.93 | 2.53 | 3.448 (4) | 169 |
C25—H25A···O29 | 0.96 | 2.56 | 3.415 (5) | 149 |
C25—H25B···Cg4iv | 0.96 | 2.62 | 3.487 (4) | 151 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H18NO2+·CF3O3S− |
Mr | 477.45 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 13.2686 (6), 8.4788 (4), 20.4078 (10) |
β (°) | 106.749 (5) |
V (Å3) | 2198.51 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.50 × 0.40 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini R Ultra Ruby CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2008) |
Tmin, Tmax | 0.869, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12172, 3892, 2096 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.137, 0.95 |
No. of reflections | 3892 |
No. of parameters | 299 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.19 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), CrysAlis RED, SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Cg4 is the centroid of the C18–C23 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O27i | 0.93 | 2.57 | 3.314 (5) | 137 |
C4—H4···O29i | 0.93 | 2.44 | 3.319 (4) | 159 |
C5—H5···O28 | 0.93 | 2.44 | 3.364 (5) | 171 |
C6—H6···O28ii | 0.93 | 2.56 | 3.342 (5) | 142 |
C23—H23···O27iii | 0.93 | 2.53 | 3.448 (4) | 169 |
C25—H25A···O29 | 0.96 | 2.56 | 3.415 (5) | 149 |
C25—H25B···Cg4iv | 0.96 | 2.62 | 3.487 (4) | 151 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1. |
X | I | J | I···J | X···J | X–I···J |
C30 | F31 | Cg2i | 3.420 (3) | 4.044 (4) | 108.9 (2) |
C30 | F32 | Cg1i | 3.441 (3) | 4.032 (4) | 107.1 (2) |
C30 | F32 | Cg2i | 3.788 (4) | 4.044 (4) | 91.5 (2) |
C30 | F33 | Cg1i | 3.669 (3) | 4.032 (4) | 96.2 (2) |
Symmetry code: (i) –x + 3/2, y + 1/2, –z + 1/2. Notes: Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 rings, respectively. |
I | J | CgI···CgJ | Dihedral angle | CgI_Perp | CgI_Offset |
3 | 4v | 3.913 (2) | 4.80 (17) | 3.472 (2) | 1.805 (2) |
4 | 3v | 3.913 (2) | 4.80 (17) | 3.565 (2) | 1.613 (2) |
Symmetry code: (v) –x + 1, –y, –z + 1. Notes: Cg3 and Cg4 are the centroids of the C5–C8/C13/C14 and C18–C23 rings, respectively. CgI···CgJ is the distance between ring centroids. The dihedral angle is that between the planes of the rings I and J. CgI_Perp is the perpendicular distance of CgI from ring J. CgI_Offset is the distance between CgI and perpendicular projection of CgJ on ring I. |
Acknowledgements
This study was financed by the State Funds for Scientific Research (grant No. N204 123 32/3143, contract No. 3143/H03/2007/32, of the Polish Ministry of Research and Higher Education) for the period 2007–2010.
References
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9-(Phenoxycarbonyl)-10-methylacridinium salts appear to be convenient chemiluminescent indicators or the chemiluminogenic fragments of chemiluminescent labels (Zomer & Jacquemijns, 2001), which are widely applied in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Roda et al., 2003; Brown et al., 2009). Oxidation of the cations of these salts with hydrogen peroxide in alkaline media is accompanied by the removal of the phenoxycarbonyl fragment and the conversion of the remaining part of the molecule to electronically excited, light emitting 10-methyl-9-acridinone (Rak et al., 1999; Zomer & Jacquemijns, 2001). The efficiency of chemiluminescence – crucial for analytical applications – is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). This prompted us to undertake investigations on derivatives substituted in this fragment. Here we present the structure of 9-(4-methylphenoxy)carbonyl-10-methylacridinium trifluoromethanesulfonate, a structural isomer of the 2-methyl substituted salt, whose structure has already been refined (Sikorski et al., 2006).
In the cation of the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the acridinium moiety are typical of acridine-based derivatives (Sikorski et al., 2006; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0386 (3) Å and 0.0017 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 3.0 (1)°. The carboxyl group is twisted at an angle of 83.1 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (remain at an angle of 0.0 (1)°) or inclined at an angle of 75.2 (1)° in the lattice.
In the crystal structure, the adjacent cations are linked through C–H···π (Table 1, Fig. 2) and π–π (involving acridine and phenyl moieties) (Table 3, Fig. 2) interactions, and cations and anions are connected by multidirectional C–H···O (Table 1, Figs. 1 and 2) and C–F···π (Table 2, Fig. 2) interactions. The C–H···O interactions are of the hydrogen bond type (Bianchi et al. 2004; Novoa et al., 2006). The C–H···π interactions should be of an attractive nature (Takahashi et al., 2001), like the C–F···π (Dorn et al., 2005) and π–π (Hunter et al., 2001) interactions. The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.