The title compounds, C
21H
14Cl
2NO
2+·CF
3O
3S
−, (I), and C
20H
11Cl
2NO
2, (II), form triclinic crystals. Adjacent cations of (I) are oriented either parallel or antiparallel; in the latter case, they are related by a centre of symmetry. Together with the CF
3SO
3− anions, the antiparallel-oriented cations of (I) form layers in which the molecules are linked
via a network of C—H
O and π–π interactions (between the benzene rings). These layers, in turn, are linked
via a network of multidirectional π–π interactions between the acridine rings, and the whole lattice is stabilized by electrostatic interactions between ions. Adjacent molecules of (II) are oriented either parallel or antiparallel; in the latter case, they are related by a centre of symmetry. Parallel-oriented molecules are arranged in chains stabilized
via C—H
Cl interactions. These chains are oriented either parallel or antiparallel and are stabilized, in the latter case,
via multidirectional π–π interactions and more generally
via dispersive interactions. Acridine and independent benzene moieties lie parallel in the lattices of (I) and (II), and are mutually oriented at an angle of 33.4 (2)° in (I) and 9.3 (2)° in (II).
Supporting information
CCDC references: 269041; 269042
Compound (II) was synthesized by the conversion of commercially available acridine-9-carboxylic acid to the acid chloride (heating the former compound with excess thionyl chloride), and by the reaction of the latter with 2,6-dichlorophenol (Sato, 1996). The crude product was purified chromatographically [SiO2, cyclohexane–ethyl acetate, 1/1 ((v/v)]. Elemental analysis (% found/calculated): C 81.1/80.7, H 5.1/5.2, N 4.3/4.3. Yellow crystals suitable for X-ray investigations were grown from cyclohexane (m.p. 515–517 K). Compound (I) was obtained upon treating compound (II) with a tenfold molar excess of methyl trifluoromethanesulfonate dissolved in dichloromethane. The product was purified by repeated recrystallization from absolute ethanol. Yellow crystals suitable for X-ray investigations were grown from absolute ethanol (m.p. 404–405 K).
The methyl H atoms in (I) were located from difference Fourier syntheses and refined as a rigid rotating group, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C); the location of these atoms was assumed in three unique positions with an occupancy factor of 0.5. Other H atoms were placed geometrically and refined using a riding model, with C—H distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: KM-4 Software (Kuma Diffraction, 1989); cell refinement: KM-4 Software; data reduction: KM-4 Software; 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 and PLATON (Spek, 2003).
(I) 9-[2,6-Dichlorophenoxy)carbonyl]-10-methylacridinium trifluoromethanesulfonate
top
Crystal data top
C21H14Cl2NO2+·CF3O3S− | Z = 2 |
Mr = 532.31 | F(000) = 540 |
Triclinic, P1 | Dx = 1.621 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.434 (2) Å | Cell parameters from 50 reflections |
b = 10.905 (2) Å | θ = 2.1–25.5° |
c = 12.260 (2) Å | µ = 0.46 mm−1 |
α = 103.14 (3)° | T = 290 K |
β = 103.40 (3)° | Prism, yellow |
γ = 109.51 (3)° | 0.5 × 0.4 × 0.3 mm |
V = 1090.8 (6) Å3 | |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.016 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.1° |
Graphite monochromator | h = −11→11 |
θ/2θ scans | k = −13→12 |
4264 measured reflections | l = 0→14 |
4064 independent reflections | 3 standard reflections every 200 reflections |
2056 reflections with I > 2σ(I) | intensity decay: 1.7% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.052P)2 + 0.5298P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
4064 reflections | Δρmax = 0.24 e Å−3 |
309 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0037 (1) |
Crystal data top
C21H14Cl2NO2+·CF3O3S− | γ = 109.51 (3)° |
Mr = 532.31 | V = 1090.8 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.434 (2) Å | Mo Kα radiation |
b = 10.905 (2) Å | µ = 0.46 mm−1 |
c = 12.260 (2) Å | T = 290 K |
α = 103.14 (3)° | 0.5 × 0.4 × 0.3 mm |
β = 103.40 (3)° | |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.016 |
4264 measured reflections | 3 standard reflections every 200 reflections |
4064 independent reflections | intensity decay: 1.7% |
2056 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.24 e Å−3 |
4064 reflections | Δρmin = −0.25 e Å−3 |
309 parameters | |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | −0.0669 (4) | 0.7036 (3) | −0.0199 (3) | 0.0440 (8) | |
H1 | −0.1535 | 0.7113 | 0.0002 | 0.053* | |
C2 | −0.0564 (4) | 0.7100 (3) | −0.1257 (3) | 0.0489 (8) | |
H2 | −0.1359 | 0.7205 | −0.1788 | 0.059* | |
C3 | 0.0757 (4) | 0.7007 (3) | −0.1561 (3) | 0.0505 (9) | |
H3 | 0.0828 | 0.7066 | −0.2293 | 0.061* | |
C4 | 0.1920 (4) | 0.6835 (3) | −0.0819 (3) | 0.0460 (8) | |
H4 | 0.2779 | 0.6776 | −0.1042 | 0.055* | |
C5 | 0.4003 (4) | 0.6046 (4) | 0.2824 (4) | 0.0590 (10) | |
H5 | 0.4813 | 0.5907 | 0.2574 | 0.071* | |
C6 | 0.3887 (5) | 0.5918 (4) | 0.3865 (4) | 0.0659 (11) | |
H6 | 0.4634 | 0.5703 | 0.4332 | 0.079* | |
C7 | 0.2688 (5) | 0.6096 (4) | 0.4268 (4) | 0.0646 (11) | |
H7 | 0.2656 | 0.6022 | 0.5004 | 0.078* | |
C8 | 0.1566 (4) | 0.6378 (4) | 0.3594 (3) | 0.0515 (9) | |
H8 | 0.0747 | 0.6470 | 0.3859 | 0.062* | |
C9 | 0.0468 (3) | 0.6788 (3) | 0.1743 (3) | 0.0364 (7) | |
N10 | 0.2991 (3) | 0.6557 (3) | 0.1054 (2) | 0.0416 (6) | |
C11 | 0.0516 (3) | 0.6854 (3) | 0.0623 (3) | 0.0363 (7) | |
C12 | 0.1833 (3) | 0.6745 (3) | 0.0287 (3) | 0.0368 (7) | |
C13 | 0.1623 (4) | 0.6535 (3) | 0.2486 (3) | 0.0393 (7) | |
C14 | 0.2893 (4) | 0.6395 (3) | 0.2103 (3) | 0.0414 (8) | |
C15 | −0.0854 (4) | 0.6984 (3) | 0.2139 (3) | 0.0381 (7) | |
O16 | −0.0249 (2) | 0.8084 (2) | 0.31341 (19) | 0.0424 (5) | |
O17 | −0.2238 (3) | 0.6294 (2) | 0.1644 (2) | 0.0565 (6) | |
C18 | −0.1292 (4) | 0.8558 (3) | 0.3550 (3) | 0.0427 (8) | |
C19 | −0.1791 (4) | 0.8213 (4) | 0.4445 (3) | 0.0519 (9) | |
C20 | −0.2653 (5) | 0.8826 (4) | 0.4951 (4) | 0.0634 (11) | |
H20 | −0.2975 | 0.8599 | 0.5567 | 0.076* | |
C21 | −0.3024 (4) | 0.9775 (4) | 0.4526 (4) | 0.0689 (12) | |
H21 | −0.3586 | 1.0207 | 0.4874 | 0.083* | |
C22 | −0.2592 (5) | 1.0111 (4) | 0.3601 (4) | 0.0660 (11) | |
H22 | −0.2884 | 1.0739 | 0.3309 | 0.079* | |
C23 | −0.1712 (4) | 0.9493 (3) | 0.3115 (3) | 0.0511 (9) | |
Cl24 | −0.13500 (15) | 0.69876 (12) | 0.49515 (10) | 0.0778 (4) | |
Cl25 | −0.11251 (16) | 0.98830 (12) | 0.19676 (11) | 0.0830 (4) | |
C26 | 0.4409 (4) | 0.6552 (5) | 0.0734 (4) | 0.0756 (13) | |
H26A | 0.4254 | 0.6561 | −0.0065 | 0.113* | 0.50 |
H26B | 0.4558 | 0.5737 | 0.0792 | 0.113* | 0.50 |
H26C | 0.5336 | 0.7354 | 0.1269 | 0.113* | 0.50 |
H26D | 0.5178 | 0.6540 | 0.1396 | 0.113* | 0.50 |
H26E | 0.4874 | 0.7364 | 0.0538 | 0.113* | 0.50 |
H26F | 0.4096 | 0.5747 | 0.0062 | 0.113* | 0.50 |
S27 | 0.52548 (11) | 0.74719 (9) | 0.76454 (8) | 0.0509 (3) | |
O28 | 0.5567 (4) | 0.6935 (3) | 0.8590 (2) | 0.0763 (8) | |
O29 | 0.3644 (3) | 0.7329 (3) | 0.7195 (2) | 0.0702 (8) | |
O30 | 0.5959 (3) | 0.7163 (3) | 0.6771 (2) | 0.0666 (7) | |
C31 | 0.6358 (5) | 0.9305 (5) | 0.8383 (4) | 0.0722 (12) | |
F32 | 0.6300 (4) | 0.9984 (3) | 0.7604 (3) | 0.1158 (10) | |
F33 | 0.5793 (4) | 0.9798 (3) | 0.9165 (3) | 0.1303 (13) | |
F34 | 0.7878 (3) | 0.9646 (3) | 0.8919 (3) | 0.1120 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0406 (19) | 0.0442 (19) | 0.055 (2) | 0.0234 (16) | 0.0162 (16) | 0.0208 (17) |
C2 | 0.053 (2) | 0.046 (2) | 0.047 (2) | 0.0224 (17) | 0.0092 (17) | 0.0196 (16) |
C3 | 0.067 (2) | 0.044 (2) | 0.048 (2) | 0.0245 (18) | 0.0265 (19) | 0.0198 (17) |
C4 | 0.045 (2) | 0.0438 (19) | 0.056 (2) | 0.0202 (16) | 0.0255 (17) | 0.0162 (16) |
C5 | 0.049 (2) | 0.061 (2) | 0.064 (3) | 0.036 (2) | 0.0055 (19) | 0.010 (2) |
C6 | 0.067 (3) | 0.065 (3) | 0.062 (3) | 0.039 (2) | −0.001 (2) | 0.021 (2) |
C7 | 0.081 (3) | 0.067 (3) | 0.057 (2) | 0.042 (2) | 0.016 (2) | 0.029 (2) |
C8 | 0.058 (2) | 0.056 (2) | 0.047 (2) | 0.0308 (19) | 0.0136 (18) | 0.0206 (18) |
C9 | 0.0324 (17) | 0.0310 (16) | 0.0446 (18) | 0.0124 (13) | 0.0116 (14) | 0.0123 (14) |
N10 | 0.0319 (15) | 0.0428 (15) | 0.0467 (16) | 0.0181 (12) | 0.0118 (13) | 0.0059 (13) |
C11 | 0.0301 (16) | 0.0302 (16) | 0.0451 (19) | 0.0113 (13) | 0.0100 (14) | 0.0105 (14) |
C12 | 0.0319 (17) | 0.0317 (16) | 0.0447 (18) | 0.0123 (14) | 0.0135 (15) | 0.0092 (14) |
C13 | 0.0421 (18) | 0.0354 (17) | 0.0395 (18) | 0.0183 (14) | 0.0094 (15) | 0.0112 (14) |
C14 | 0.0353 (17) | 0.0362 (18) | 0.0452 (19) | 0.0184 (15) | 0.0035 (15) | 0.0044 (15) |
C15 | 0.038 (2) | 0.0375 (18) | 0.0413 (18) | 0.0167 (16) | 0.0130 (16) | 0.0160 (15) |
O16 | 0.0390 (12) | 0.0436 (12) | 0.0466 (13) | 0.0196 (10) | 0.0169 (10) | 0.0120 (11) |
O17 | 0.0369 (14) | 0.0555 (15) | 0.0679 (16) | 0.0157 (13) | 0.0177 (12) | 0.0087 (13) |
C18 | 0.0367 (18) | 0.0398 (18) | 0.051 (2) | 0.0151 (15) | 0.0194 (16) | 0.0109 (16) |
C19 | 0.049 (2) | 0.049 (2) | 0.061 (2) | 0.0181 (17) | 0.0264 (19) | 0.0181 (18) |
C20 | 0.061 (2) | 0.064 (2) | 0.070 (3) | 0.020 (2) | 0.042 (2) | 0.017 (2) |
C21 | 0.055 (2) | 0.068 (3) | 0.089 (3) | 0.031 (2) | 0.039 (2) | 0.010 (2) |
C22 | 0.057 (2) | 0.060 (2) | 0.094 (3) | 0.037 (2) | 0.031 (2) | 0.023 (2) |
C23 | 0.053 (2) | 0.046 (2) | 0.061 (2) | 0.0225 (17) | 0.0256 (18) | 0.0209 (17) |
Cl24 | 0.1024 (9) | 0.0797 (8) | 0.0893 (8) | 0.0480 (7) | 0.0570 (7) | 0.0540 (6) |
Cl25 | 0.1213 (10) | 0.0848 (8) | 0.0961 (9) | 0.0654 (8) | 0.0657 (8) | 0.0603 (7) |
C26 | 0.044 (2) | 0.114 (4) | 0.070 (3) | 0.044 (2) | 0.021 (2) | 0.014 (2) |
S27 | 0.0560 (6) | 0.0562 (6) | 0.0501 (5) | 0.0279 (5) | 0.0254 (4) | 0.0195 (4) |
O28 | 0.092 (2) | 0.094 (2) | 0.0695 (18) | 0.0475 (18) | 0.0392 (16) | 0.0473 (17) |
O29 | 0.0518 (16) | 0.086 (2) | 0.0701 (18) | 0.0310 (15) | 0.0175 (14) | 0.0197 (15) |
O30 | 0.0839 (19) | 0.0775 (18) | 0.0601 (16) | 0.0458 (16) | 0.0422 (15) | 0.0238 (14) |
C31 | 0.067 (3) | 0.068 (3) | 0.084 (3) | 0.030 (2) | 0.030 (3) | 0.020 (3) |
F32 | 0.128 (3) | 0.0773 (19) | 0.157 (3) | 0.0452 (18) | 0.051 (2) | 0.058 (2) |
F33 | 0.133 (3) | 0.097 (2) | 0.133 (3) | 0.039 (2) | 0.069 (2) | −0.0239 (19) |
F34 | 0.0699 (19) | 0.093 (2) | 0.133 (3) | 0.0135 (15) | 0.0147 (17) | 0.0143 (18) |
Geometric parameters (Å, º) top
C1—C2 | 1.338 (4) | C15—O17 | 1.187 (4) |
C1—C11 | 1.421 (4) | O16—C18 | 1.396 (3) |
C1—H1 | 0.9300 | C18—C19 | 1.369 (4) |
C2—C3 | 1.409 (5) | C18—C23 | 1.378 (5) |
C2—H2 | 0.9300 | C19—C20 | 1.380 (5) |
C3—C4 | 1.349 (5) | C19—Cl24 | 1.725 (4) |
C3—H3 | 0.9300 | C20—C21 | 1.366 (5) |
C4—C12 | 1.401 (4) | C20—H20 | 0.9300 |
C4—H4 | 0.9300 | C21—C22 | 1.375 (6) |
C5—C6 | 1.340 (5) | C21—H21 | 0.9300 |
C5—C14 | 1.418 (5) | C22—C23 | 1.386 (5) |
C5—H5 | 0.9300 | C22—H22 | 0.9300 |
C6—C7 | 1.387 (5) | C23—Cl25 | 1.715 (3) |
C6—H6 | 0.9300 | C26—H26A | 0.9600 |
C7—C8 | 1.351 (5) | C26—H26B | 0.9600 |
C7—H7 | 0.9300 | C26—H26C | 0.9600 |
C8—C13 | 1.418 (4) | C26—H26D | 0.9600 |
C8—H8 | 0.9300 | C26—H26E | 0.9600 |
C9—C13 | 1.395 (4) | C26—H26F | 0.9600 |
C9—C11 | 1.403 (4) | S27—O30 | 1.421 (2) |
C9—C15 | 1.499 (4) | S27—O28 | 1.427 (3) |
N10—C14 | 1.357 (4) | S27—O29 | 1.433 (3) |
N10—C12 | 1.372 (4) | S27—C31 | 1.802 (5) |
N10—C26 | 1.480 (4) | C31—F33 | 1.299 (5) |
C11—C12 | 1.428 (4) | C31—F34 | 1.313 (5) |
C13—C14 | 1.424 (4) | C31—F32 | 1.337 (5) |
C15—O16 | 1.344 (4) | | |
| | | |
C2—C1—C11 | 121.4 (3) | C18—C19—C20 | 121.1 (3) |
C2—C1—H1 | 119.3 | C18—C19—Cl24 | 120.0 (3) |
C11—C1—H1 | 119.3 | C20—C19—Cl24 | 118.9 (3) |
C1—C2—C3 | 119.7 (3) | C21—C20—C19 | 118.4 (4) |
C1—C2—H2 | 120.2 | C21—C20—H20 | 120.8 |
C3—C2—H2 | 120.2 | C19—C20—H20 | 120.8 |
C4—C3—C2 | 121.7 (3) | C20—C21—C22 | 122.1 (3) |
C4—C3—H3 | 119.1 | C20—C21—H21 | 118.9 |
C2—C3—H3 | 119.1 | C22—C21—H21 | 118.9 |
C3—C4—C12 | 119.9 (3) | C21—C22—C23 | 118.4 (4) |
C3—C4—H4 | 120.0 | C21—C22—H22 | 120.8 |
C12—C4—H4 | 120.0 | C23—C22—H22 | 120.8 |
C6—C5—C14 | 120.0 (3) | C18—C23—C22 | 120.4 (3) |
C6—C5—H5 | 120.0 | C18—C23—Cl25 | 119.1 (2) |
C14—C5—H5 | 120.0 | C22—C23—Cl25 | 120.5 (3) |
C5—C6—C7 | 122.2 (3) | N10—C26—H26A | 109.5 |
C5—C6—H6 | 118.9 | N10—C26—H26B | 109.5 |
C7—C6—H6 | 118.9 | H26A—C26—H26B | 109.5 |
C8—C7—C6 | 120.1 (4) | N10—C26—H26C | 109.5 |
C8—C7—H7 | 120.0 | H26A—C26—H26C | 109.5 |
C6—C7—H7 | 120.0 | H26B—C26—H26C | 109.5 |
C7—C8—C13 | 120.7 (3) | N10—C26—H26D | 109.5 |
C7—C8—H8 | 119.7 | H26A—C26—H26D | 141.1 |
C13—C8—H8 | 119.7 | H26B—C26—H26D | 56.3 |
C13—C9—C11 | 121.0 (3) | H26C—C26—H26D | 56.3 |
C13—C9—C15 | 119.9 (3) | N10—C26—H26E | 109.5 |
C11—C9—C15 | 119.1 (3) | H26A—C26—H26E | 56.3 |
C14—N10—C12 | 122.3 (2) | H26B—C26—H26E | 141.1 |
C14—N10—C26 | 118.9 (3) | H26C—C26—H26E | 56.3 |
C12—N10—C26 | 118.8 (3) | H26D—C26—H26E | 109.5 |
C9—C11—C1 | 123.7 (3) | N10—C26—H26F | 109.5 |
C9—C11—C12 | 118.4 (3) | H26A—C26—H26F | 56.3 |
C1—C11—C12 | 117.9 (3) | H26B—C26—H26F | 56.3 |
N10—C12—C4 | 121.1 (3) | H26C—C26—H26F | 141.1 |
N10—C12—C11 | 119.5 (3) | H26D—C26—H26F | 109.5 |
C4—C12—C11 | 119.4 (3) | H26E—C26—H26F | 109.5 |
C9—C13—C8 | 122.7 (3) | O30—S27—O28 | 114.62 (17) |
C9—C13—C14 | 118.7 (3) | O30—S27—O29 | 115.43 (16) |
C8—C13—C14 | 118.5 (3) | O28—S27—O29 | 115.03 (17) |
N10—C14—C5 | 121.7 (3) | O30—S27—C31 | 103.60 (19) |
N10—C14—C13 | 119.8 (3) | O28—S27—C31 | 102.5 (2) |
C5—C14—C13 | 118.5 (3) | O29—S27—C31 | 103.17 (19) |
C9—C15—O16 | 110.1 (3) | F33—C31—F34 | 107.9 (4) |
C9—C15—O17 | 125.6 (3) | F33—C31—F32 | 106.7 (4) |
C15—O16—C18 | 118.8 (2) | F34—C31—F32 | 105.9 (4) |
O16—C15—O17 | 124.2 (3) | F33—C31—S27 | 112.4 (3) |
C19—C18—C23 | 119.5 (3) | F34—C31—S27 | 112.6 (3) |
C19—C18—O16 | 121.7 (3) | F32—C31—S27 | 111.0 (3) |
C23—C18—O16 | 118.5 (3) | | |
| | | |
C11—C1—C2—C3 | −1.0 (5) | C8—C13—C14—N10 | −179.1 (3) |
C1—C2—C3—C4 | 0.9 (5) | C9—C13—C14—C5 | −175.8 (3) |
C2—C3—C4—C12 | −0.1 (5) | C8—C13—C14—C5 | 2.7 (5) |
C14—C5—C6—C7 | 1.0 (6) | C13—C9—C15—O17 | −120.2 (4) |
C5—C6—C7—C8 | 1.5 (6) | C13—C9—C15—O16 | 61.1 (4) |
C6—C7—C8—C13 | −1.8 (6) | C11—C9—C15—O16 | −119.3 (3) |
C13—C9—C11—C1 | 176.6 (3) | O17—C15—O16—C18 | −7.8 (4) |
C15—C9—C11—C1 | −3.0 (4) | C9—C15—O16—C18 | 171.0 (2) |
C13—C9—C11—C12 | −4.0 (4) | C11—C9—C15—O17 | 59.5 (4) |
C15—C9—C11—C12 | 176.4 (3) | C15—O16—C18—C19 | 98.6 (4) |
C2—C1—C11—C9 | 179.7 (3) | C15—O16—C18—C23 | −87.2 (4) |
C2—C1—C11—C12 | 0.2 (5) | C23—C18—C19—C20 | −2.6 (5) |
C14—N10—C12—C4 | −176.5 (3) | O16—C18—C19—C20 | 171.6 (3) |
C26—N10—C12—C4 | 4.5 (4) | C23—C18—C19—Cl24 | 177.1 (3) |
C14—N10—C12—C11 | 3.6 (4) | O16—C18—C19—Cl24 | −8.7 (5) |
C26—N10—C12—C11 | −175.4 (3) | C18—C19—C20—C21 | 1.0 (6) |
C3—C4—C12—N10 | 179.4 (3) | Cl24—C19—C20—C21 | −178.7 (3) |
C3—C4—C12—C11 | −0.7 (5) | C19—C20—C21—C22 | 1.3 (6) |
C9—C11—C12—N10 | 1.1 (4) | C20—C21—C22—C23 | −2.0 (6) |
C1—C11—C12—N10 | −179.5 (3) | C19—C18—C23—C22 | 1.9 (5) |
C9—C11—C12—C4 | −178.8 (3) | O16—C18—C23—C22 | −172.5 (3) |
C1—C11—C12—C4 | 0.7 (4) | C19—C18—C23—Cl25 | −178.3 (3) |
C11—C9—C13—C8 | −176.1 (3) | O16—C18—C23—Cl25 | 7.3 (4) |
C15—C9—C13—C8 | 3.5 (5) | C21—C22—C23—C18 | 0.3 (6) |
C11—C9—C13—C14 | 2.3 (4) | C21—C22—C23—Cl25 | −179.5 (3) |
C15—C9—C13—C14 | −178.1 (3) | O30—S27—C31—F33 | 175.1 (3) |
C7—C8—C13—C9 | 178.2 (3) | O28—S27—C31—F33 | −65.3 (4) |
C7—C8—C13—C14 | −0.3 (5) | O29—S27—C31—F33 | 54.5 (4) |
C12—N10—C14—C5 | 172.7 (3) | O30—S27—C31—F34 | −62.8 (4) |
C26—N10—C14—C5 | −8.2 (5) | O28—S27—C31—F34 | 56.8 (4) |
C12—N10—C14—C13 | −5.4 (4) | O29—S27—C31—F34 | 176.6 (3) |
C26—N10—C14—C13 | 173.7 (3) | O30—S27—C31—F32 | 55.8 (3) |
C6—C5—C14—N10 | 178.8 (3) | O28—S27—C31—F32 | 175.3 (3) |
C6—C5—C14—C13 | −3.0 (5) | O29—S27—C31—F32 | −64.9 (3) |
C9—C13—C14—N10 | 2.3 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O29 | 0.93 | 2.52 | 3.316 (5) | 144 |
C20—H20···O30i | 0.93 | 2.52 | 3.404 (5) | 160 |
Symmetry code: (i) x−1, y, z. |
(II) 2,6-dichlorophenyl acridine-9-carboxylate
top
Crystal data top
C20H11Cl2NO2 | Z = 2 |
Mr = 368.20 | F(000) = 376 |
Triclinic, P1 | Dx = 1.488 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.004 (2) Å | Cell parameters from 50 reflections |
b = 9.423 (2) Å | θ = 2.4–25.5° |
c = 12.428 (2) Å | µ = 0.41 mm−1 |
α = 101.92 (3)° | T = 290 K |
β = 107.04 (3)° | Prism, yellow |
γ = 105.37 (3)° | 0.4 × 0.3 × 0.3 mm |
V = 822.0 (4) Å3 | |
Data collection top
Kuma KM4 diffractometer | Rint = 0.013 |
Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.4° |
Graphite monochromator | h = −9→9 |
θ/2θ scans | k = −11→10 |
3188 measured reflections | l = −9→15 |
3040 independent reflections | 3 standard reflections every 200 reflections |
2004 reflections with I > 2σ(I) | intensity decay: 0.9% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0508P)2 + 0.1815P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
3040 reflections | Δρmax = 0.20 e Å−3 |
227 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
Crystal data top
C20H11Cl2NO2 | γ = 105.37 (3)° |
Mr = 368.20 | V = 822.0 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.004 (2) Å | Mo Kα radiation |
b = 9.423 (2) Å | µ = 0.41 mm−1 |
c = 12.428 (2) Å | T = 290 K |
α = 101.92 (3)° | 0.4 × 0.3 × 0.3 mm |
β = 107.04 (3)° | |
Data collection top
Kuma KM4 diffractometer | Rint = 0.013 |
3188 measured reflections | 3 standard reflections every 200 reflections |
3040 independent reflections | intensity decay: 0.9% |
2004 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.20 e Å−3 |
3040 reflections | Δρmin = −0.18 e Å−3 |
227 parameters | |
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 | x | y | z | Uiso*/Ueq | |
C1 | 0.6880 (3) | 0.3703 (3) | 0.83673 (19) | 0.0492 (5) | |
H1 | 0.6357 | 0.2846 | 0.7693 | 0.059* | |
C2 | 0.6563 (3) | 0.3573 (3) | 0.9359 (2) | 0.0608 (6) | |
H2 | 0.5828 | 0.2627 | 0.9362 | 0.073* | |
C3 | 0.7339 (4) | 0.4860 (3) | 1.0389 (2) | 0.0641 (7) | |
H3 | 0.7099 | 0.4755 | 1.1062 | 0.077* | |
C4 | 0.8414 (3) | 0.6230 (3) | 1.04120 (19) | 0.0566 (6) | |
H4 | 0.8918 | 0.7061 | 1.1103 | 0.068* | |
C5 | 1.1415 (3) | 0.9504 (2) | 0.8600 (2) | 0.0551 (6) | |
H5 | 1.1905 | 1.0306 | 0.9307 | 0.066* | |
C6 | 1.1804 (3) | 0.9757 (3) | 0.7657 (2) | 0.0606 (6) | |
H6 | 1.2552 | 1.0736 | 0.7722 | 0.073* | |
C7 | 1.1097 (3) | 0.8565 (3) | 0.6578 (2) | 0.0568 (6) | |
H7 | 1.1399 | 0.8758 | 0.5942 | 0.068* | |
C8 | 0.9984 (3) | 0.7143 (2) | 0.64596 (19) | 0.0450 (5) | |
H8 | 0.9520 | 0.6367 | 0.5739 | 0.054* | |
C9 | 0.8381 (2) | 0.5367 (2) | 0.73545 (16) | 0.0348 (4) | |
N10 | 0.9902 (2) | 0.7829 (2) | 0.94793 (14) | 0.0470 (4) | |
C11 | 0.8002 (3) | 0.5134 (2) | 0.83442 (16) | 0.0385 (4) | |
C12 | 0.8799 (3) | 0.6437 (3) | 0.93970 (17) | 0.0444 (5) | |
C13 | 0.9513 (3) | 0.6813 (2) | 0.74146 (16) | 0.0374 (4) | |
C14 | 1.0262 (3) | 0.8022 (2) | 0.85227 (17) | 0.0428 (5) | |
C15 | 0.7641 (3) | 0.4040 (2) | 0.62374 (16) | 0.0347 (4) | |
O16 | 0.61728 (18) | 0.41472 (14) | 0.54212 (11) | 0.0383 (3) | |
O17 | 0.8239 (2) | 0.30216 (17) | 0.60825 (13) | 0.0550 (4) | |
C18 | 0.5268 (3) | 0.2967 (2) | 0.43431 (16) | 0.0372 (4) | |
C19 | 0.5516 (3) | 0.3207 (2) | 0.33332 (18) | 0.0425 (5) | |
C20 | 0.4553 (3) | 0.2082 (3) | 0.22557 (18) | 0.0524 (5) | |
H20 | 0.4735 | 0.2258 | 0.1583 | 0.063* | |
C21 | 0.3323 (3) | 0.0698 (3) | 0.2170 (2) | 0.0556 (6) | |
H21 | 0.2688 | −0.0068 | 0.1442 | 0.067* | |
C22 | 0.3029 (3) | 0.0443 (2) | 0.3159 (2) | 0.0530 (6) | |
H22 | 0.2184 | −0.0489 | 0.3102 | 0.064* | |
C23 | 0.3995 (3) | 0.1576 (2) | 0.42378 (18) | 0.0433 (5) | |
Cl24 | 0.70330 (8) | 0.49537 (7) | 0.34268 (5) | 0.05747 (19) | |
Cl25 | 0.35667 (9) | 0.12786 (7) | 0.54652 (5) | 0.0634 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0495 (12) | 0.0498 (12) | 0.0397 (11) | 0.0088 (10) | 0.0129 (10) | 0.0127 (10) |
C2 | 0.0597 (15) | 0.0667 (16) | 0.0530 (14) | 0.0094 (12) | 0.0226 (12) | 0.0258 (12) |
C3 | 0.0728 (17) | 0.0844 (19) | 0.0444 (13) | 0.0263 (14) | 0.0294 (12) | 0.0284 (13) |
C4 | 0.0689 (16) | 0.0667 (15) | 0.0324 (11) | 0.0253 (13) | 0.0177 (11) | 0.0106 (10) |
C5 | 0.0555 (14) | 0.0377 (11) | 0.0484 (13) | 0.0027 (10) | 0.0082 (11) | −0.0014 (10) |
C6 | 0.0570 (14) | 0.0398 (12) | 0.0668 (16) | −0.0034 (10) | 0.0205 (12) | 0.0095 (11) |
C7 | 0.0558 (14) | 0.0486 (13) | 0.0588 (14) | 0.0022 (11) | 0.0267 (12) | 0.0145 (11) |
C8 | 0.0474 (12) | 0.0390 (10) | 0.0400 (11) | 0.0067 (9) | 0.0167 (9) | 0.0052 (9) |
C9 | 0.0337 (10) | 0.0341 (9) | 0.0323 (9) | 0.0111 (8) | 0.0093 (8) | 0.0066 (8) |
N10 | 0.0535 (11) | 0.0439 (10) | 0.0331 (9) | 0.0143 (8) | 0.0096 (8) | 0.0032 (7) |
C11 | 0.0383 (10) | 0.0426 (11) | 0.0311 (10) | 0.0143 (9) | 0.0091 (8) | 0.0096 (8) |
C12 | 0.0469 (12) | 0.0510 (12) | 0.0338 (10) | 0.0207 (10) | 0.0117 (9) | 0.0101 (9) |
C13 | 0.0369 (10) | 0.0346 (10) | 0.0343 (10) | 0.0109 (8) | 0.0093 (8) | 0.0053 (8) |
C14 | 0.0421 (11) | 0.0371 (10) | 0.0376 (11) | 0.0104 (9) | 0.0076 (9) | 0.0030 (9) |
C15 | 0.0362 (10) | 0.0312 (9) | 0.0335 (10) | 0.0072 (8) | 0.0139 (8) | 0.0080 (8) |
O16 | 0.0447 (8) | 0.0319 (7) | 0.0296 (7) | 0.0120 (6) | 0.0071 (6) | 0.0029 (5) |
O17 | 0.0563 (9) | 0.0460 (8) | 0.0501 (9) | 0.0248 (8) | 0.0062 (7) | −0.0005 (7) |
C18 | 0.0394 (10) | 0.0326 (10) | 0.0320 (9) | 0.0116 (8) | 0.0073 (8) | 0.0040 (8) |
C19 | 0.0439 (11) | 0.0411 (11) | 0.0388 (11) | 0.0147 (9) | 0.0133 (9) | 0.0077 (9) |
C20 | 0.0580 (14) | 0.0580 (14) | 0.0337 (11) | 0.0201 (11) | 0.0123 (10) | 0.0057 (10) |
C21 | 0.0593 (14) | 0.0460 (12) | 0.0386 (12) | 0.0148 (11) | 0.0008 (10) | −0.0034 (10) |
C22 | 0.0523 (13) | 0.0342 (10) | 0.0525 (13) | 0.0085 (10) | 0.0025 (11) | 0.0057 (10) |
C23 | 0.0469 (12) | 0.0356 (10) | 0.0389 (10) | 0.0116 (9) | 0.0075 (9) | 0.0100 (9) |
Cl24 | 0.0658 (4) | 0.0544 (3) | 0.0455 (3) | 0.0067 (3) | 0.0242 (3) | 0.0151 (2) |
Cl25 | 0.0723 (4) | 0.0515 (3) | 0.0526 (3) | 0.0003 (3) | 0.0195 (3) | 0.0210 (3) |
Geometric parameters (Å, º) top
C1—C2 | 1.352 (3) | C9—C15 | 1.500 (3) |
C1—C11 | 1.420 (3) | N10—C12 | 1.337 (3) |
C1—H1 | 0.9300 | N10—C14 | 1.339 (3) |
C2—C3 | 1.410 (4) | C11—C12 | 1.434 (3) |
C2—H2 | 0.9300 | C13—C14 | 1.435 (3) |
C3—C4 | 1.338 (4) | C15—O16 | 1.351 (2) |
C3—H3 | 0.9300 | C15—O17 | 1.187 (2) |
C4—C12 | 1.422 (3) | O16—C18 | 1.395 (2) |
C4—H4 | 0.9300 | C18—C19 | 1.381 (3) |
C5—C6 | 1.347 (3) | C18—C23 | 1.384 (3) |
C5—C14 | 1.421 (3) | C19—C20 | 1.374 (3) |
C5—H5 | 0.9300 | C19—Cl24 | 1.725 (2) |
C6—C7 | 1.406 (3) | C20—C21 | 1.372 (3) |
C6—H6 | 0.9300 | C20—H20 | 0.9300 |
C7—C8 | 1.349 (3) | C21—C22 | 1.373 (3) |
C7—H7 | 0.9300 | C21—H21 | 0.9300 |
C8—C13 | 1.414 (3) | C22—C23 | 1.378 (3) |
C8—H8 | 0.9300 | C22—H22 | 0.9300 |
C9—C13 | 1.395 (3) | C23—Cl25 | 1.719 (2) |
C9—C11 | 1.396 (3) | | |
| | | |
C2—C1—C11 | 120.7 (2) | N10—C12—C4 | 118.26 (19) |
C2—C1—H1 | 119.7 | N10—C12—C11 | 123.56 (18) |
C11—C1—H1 | 119.7 | C4—C12—C11 | 118.2 (2) |
C1—C2—C3 | 120.5 (2) | C9—C13—C8 | 123.94 (18) |
C1—C2—H2 | 119.7 | C9—C13—C14 | 117.51 (18) |
C3—C2—H2 | 119.7 | C8—C13—C14 | 118.54 (18) |
C4—C3—C2 | 121.0 (2) | N10—C14—C5 | 118.50 (19) |
C4—C3—H3 | 119.5 | N10—C14—C13 | 123.21 (19) |
C2—C3—H3 | 119.5 | C5—C14—C13 | 118.29 (19) |
C3—C4—C12 | 121.1 (2) | C9—C15—O16 | 110.75 (16) |
C3—C4—H4 | 119.5 | C9—C15—O17 | 125.26 (18) |
C12—C4—H4 | 119.5 | C15—O16—C18 | 118.14 (15) |
C6—C5—C14 | 120.6 (2) | O16—C15—O17 | 123.99 (17) |
C6—C5—H5 | 119.7 | C19—C18—C23 | 118.30 (18) |
C14—C5—H5 | 119.7 | C19—C18—O16 | 120.36 (16) |
C5—C6—C7 | 121.1 (2) | C23—C18—O16 | 121.14 (17) |
C5—C6—H6 | 119.5 | C20—C19—C18 | 120.79 (19) |
C7—C6—H6 | 119.5 | C20—C19—Cl24 | 119.77 (17) |
C8—C7—C6 | 120.4 (2) | C18—C19—Cl24 | 119.43 (15) |
C8—C7—H7 | 119.8 | C21—C20—C19 | 120.2 (2) |
C6—C7—H7 | 119.8 | C21—C20—H20 | 119.9 |
C7—C8—C13 | 121.0 (2) | C19—C20—H20 | 119.9 |
C7—C8—H8 | 119.5 | C20—C21—C22 | 120.1 (2) |
C13—C8—H8 | 119.5 | C20—C21—H21 | 120.0 |
C13—C9—C11 | 120.28 (17) | C22—C21—H21 | 120.0 |
C13—C9—C15 | 119.75 (16) | C21—C22—C23 | 119.6 (2) |
C11—C9—C15 | 119.92 (16) | C21—C22—H22 | 120.2 |
C12—N10—C14 | 118.19 (17) | C23—C22—H22 | 120.2 |
C9—C11—C1 | 124.18 (18) | C22—C23—C18 | 121.1 (2) |
C9—C11—C12 | 117.24 (18) | C22—C23—Cl25 | 119.44 (16) |
C1—C11—C12 | 118.58 (18) | C18—C23—Cl25 | 119.46 (15) |
| | | |
C11—C1—C2—C3 | 0.2 (4) | C6—C5—C14—N10 | −179.4 (2) |
C1—C2—C3—C4 | −0.6 (4) | C6—C5—C14—C13 | −0.6 (3) |
C2—C3—C4—C12 | 0.5 (4) | C9—C13—C14—N10 | −1.1 (3) |
C14—C5—C6—C7 | −0.6 (4) | C8—C13—C14—N10 | −179.99 (19) |
C5—C6—C7—C8 | 1.1 (4) | C9—C13—C14—C5 | −179.89 (19) |
C6—C7—C8—C13 | −0.5 (4) | C8—C13—C14—C5 | 1.2 (3) |
C13—C9—C11—C1 | −179.55 (19) | C13—C9—C15—O17 | 102.2 (2) |
C15—C9—C11—C1 | −2.3 (3) | C13—C9—C15—O16 | −78.4 (2) |
C13—C9—C11—C12 | 0.8 (3) | C11—C9—C15—O16 | 104.33 (19) |
C15—C9—C11—C12 | 178.04 (17) | O17—C15—O16—C18 | 2.0 (3) |
C2—C1—C11—C9 | −179.4 (2) | C9—C15—O16—C18 | −177.47 (14) |
C2—C1—C11—C12 | 0.3 (3) | C11—C9—C15—O17 | −75.1 (3) |
C14—N10—C12—C4 | −180.0 (2) | C15—O16—C18—C19 | −105.7 (2) |
C14—N10—C12—C11 | 0.8 (3) | C15—O16—C18—C23 | 79.4 (2) |
C3—C4—C12—N10 | −179.3 (2) | C23—C18—C19—C20 | −1.4 (3) |
C3—C4—C12—C11 | 0.0 (3) | O16—C18—C19—C20 | −176.40 (18) |
C9—C11—C12—N10 | −1.5 (3) | C23—C18—C19—Cl24 | 177.79 (16) |
C1—C11—C12—N10 | 178.85 (19) | O16—C18—C19—Cl24 | 2.8 (3) |
C9—C11—C12—C4 | 179.31 (19) | C18—C19—C20—C21 | 0.1 (3) |
C1—C11—C12—C4 | −0.4 (3) | Cl24—C19—C20—C21 | −179.05 (18) |
C11—C9—C13—C8 | 179.21 (19) | C19—C20—C21—C22 | 1.0 (3) |
C15—C9—C13—C8 | 2.0 (3) | C20—C21—C22—C23 | −0.9 (3) |
C11—C9—C13—C14 | 0.4 (3) | C21—C22—C23—C18 | −0.4 (3) |
C15—C9—C13—C14 | −176.88 (17) | C21—C22—C23—Cl25 | 177.83 (18) |
C7—C8—C13—C9 | −179.5 (2) | C19—C18—C23—C22 | 1.5 (3) |
C7—C8—C13—C14 | −0.7 (3) | O16—C18—C23—C22 | 176.52 (18) |
C12—N10—C14—C5 | 179.29 (19) | C19—C18—C23—Cl25 | −176.73 (15) |
C12—N10—C14—C13 | 0.5 (3) | O16—C18—C23—Cl25 | −1.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Cl25i | 0.93 | 2.83 | 3.570 (3) | 137 |
Symmetry code: (i) x+1, y+1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C21H14Cl2NO2+·CF3O3S− | C20H11Cl2NO2 |
Mr | 532.31 | 368.20 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 290 | 290 |
a, b, c (Å) | 9.434 (2), 10.905 (2), 12.260 (2) | 8.004 (2), 9.423 (2), 12.428 (2) |
α, β, γ (°) | 103.14 (3), 103.40 (3), 109.51 (3) | 101.92 (3), 107.04 (3), 105.37 (3) |
V (Å3) | 1090.8 (6) | 822.0 (4) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.46 | 0.41 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 | 0.4 × 0.3 × 0.3 |
|
Data collection |
Diffractometer | Kuma KM-4 diffractometer | Kuma KM4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4264, 4064, 2056 | 3188, 3040, 2004 |
Rint | 0.016 | 0.013 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.121, 1.00 | 0.033, 0.098, 1.01 |
No. of reflections | 4064 | 3040 |
No. of parameters | 309 | 227 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.25 | 0.20, −0.18 |
Selected geometric parameters (Å, º) for (I) topC9—C11 | 1.403 (4) | C15—O17 | 1.187 (4) |
C9—C15 | 1.499 (4) | O16—C18 | 1.396 (3) |
N10—C12 | 1.372 (4) | C18—C19 | 1.369 (4) |
N10—C26 | 1.480 (4) | C19—Cl24 | 1.725 (4) |
C15—O16 | 1.344 (4) | | |
| | | |
C9—C15—O16 | 110.1 (3) | C15—O16—C18 | 118.8 (2) |
C9—C15—O17 | 125.6 (3) | O16—C15—O17 | 124.2 (3) |
| | | |
C9—C15—O16—C18 | 171.0 (2) | C15—O16—C18—C19 | 98.6 (4) |
C11—C9—C15—O17 | 59.5 (4) | O16—C18—C19—Cl24 | −8.7 (5) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O29 | 0.93 | 2.52 | 3.316 (5) | 144 |
C20—H20···O30i | 0.93 | 2.52 | 3.404 (5) | 160 |
Symmetry code: (i) x−1, y, z. |
π–π interactions (Å, °) in (I) topCgI | CgJ | Cg···Cg | Dihedral angle | Interplanar distance | Offset |
Cg1 | Cg2ii | 3.532 (2) | 1.9 | 3.488 (3) | 0.556 (2) |
Cg2 | Cg1ii | 3.532 (2) | 1.9 | 3.482 (3) | 0.556 (2) |
Cg2 | Cg3ii | 3.956 (2) | 5.5 | 3.510 (3) | 1.825 (2) |
Cg3 | Cg2ii | 3.956 (2) | 5.5 | 3.334 (3) | 2.130 (2) |
Cg4 | Cg4iii | 3.788 (2) | 0.0 | 3.473 (3) | 1.512 (2) |
Symmetry codes: (ii) −x, 1 − y, −z; (iii) −x, 2 − y, 1 − z. Cg represents the centre of gravity of the following rings: Cg1 (ring delineated by atoms N10, C12, C11,C9, C13 and C14), Cg2 (ring delineated by atoms C1, C2, C3, C4, C12 and C11), Cg3 (ring delineated by atoms C5, C6, C7, C8, C13 and C14), Cg4 (ring delineated by atoms C18, C19, C20, C21, C22 and C23). Cg···Cg is the distance between ring centroids. Dihedral angle is that between the planes of CgI and CgJ. Interplanar distance is the perpendicular distance of CgI from ring J. Offset is the perpendicular distance of ring I from ring J. |
Selected geometric parameters (Å, º) for (II) topC9—C11 | 1.396 (3) | C15—O17 | 1.187 (2) |
C9—C15 | 1.500 (3) | O16—C18 | 1.395 (2) |
N10—C12 | 1.337 (3) | C18—C19 | 1.381 (3) |
C15—O16 | 1.351 (2) | C19—Cl24 | 1.725 (2) |
| | | |
C9—C15—O16 | 110.75 (16) | C15—O16—C18 | 118.14 (15) |
C9—C15—O17 | 125.26 (18) | O16—C15—O17 | 123.99 (17) |
| | | |
C9—C15—O16—C18 | −177.47 (14) | C15—O16—C18—C19 | −105.7 (2) |
C11—C9—C15—O17 | −75.1 (3) | O16—C18—C19—Cl24 | 2.8 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Cl25i | 0.93 | 2.83 | 3.570 (3) | 137 |
Symmetry code: (i) x+1, y+1, z. |
π–π interactions (Å, °) in (II) topCgI | CgJ | Cg···Cg | Dihedral angle | Interplanar distance | Offset |
Cg1 | Cg2ii | 3.986 (2) | 0.8 | 3.466 (3) | 1.969 (2) |
Cg1 | Cg4iii | 3.754 (2) | 8.6 | 3.449 (3) | 1.482 (2) |
Cg2 | Cg1ii | 3.986 (2) | 0.8 | 3.461 (3) | 1.977 (2) |
Cg2 | Cg2ii | 3.593 (2) | 0.0 | 3.470 (3) | 0.932 (2) |
Cg3 | Cg4iii | 3.762 (2) | 8.7 | 3.418 (3) | 1.572 (2) |
Cg4 | Cg1iii | 3.754 (2) | 8.6 | 3.536 (3) | 1.260 (2) |
Cg4 | Cg3iii | 3.762 (2) | 8.7 | 3.537 (3) | 1.282 (2) |
Symmetry codes: (ii) 2 − x, 1 − y, 2 − z; (iii) 1 − x, 1 − y, 1 − z. Cg represents the centre of gravity of the following rings: Cg1 (ring delineated by atoms N10, C12, C11,C9, C13 and C14), Cg2 (ring delineated by atoms C1, C2, C3, C4, C12 and C11), Cg3 (ring delineated by atoms C5, C6, C7, C8, C13 and C14), Cg4 (ring delineated by atoms C18, C19, C20, C21, C22 and C23). Cg···Cg is the distance between ring centroids. Dihedral angle is that between planes I and J. Interplanar distance is the perpendicular distance of CgI from ring J. Offset is the perpendicular distance of ring I from ring J. |
Numerous acridine-based derivatives are important, owing to their chemiluminogenic ability and their utility as chemiluminescent indicators or fragments of chemiluminescent labels, with applications in immunoassays, nucleic acid diagnostics and quantitative assays of biomolecules, such as antigens, antibodies, hormones and enzymes, as well as DNA–RNA structural analyses (Becker et al., 1999; Dodeigne et al., 2000; Zomer & Jacquemijns, 2001). Among acridine-based chemiluminogens, phenyl acridine-9-carboxylates are the most promising analytical agents, since they exhibit relatively high quantum yields of light emission and stability (Adamczyk et al., 1999; Dodeigne et al., 2000; Razawi & McCapra, 2000; Renotte et al., 2000; Smith et al., 2000; Zomer & Jacquemijns, 2001). Continuing the search for new analytically interesting acridine-based chemiluminogens, we synthesized phenyl acridine-9-carboxylate substituted with two Cl atoms, (II), and its trifluoromethanesulfonate salt, (I), methylated at the endocyclic N atom, in order to discover how the presence of heavy Cl atoms in the phenyl fragment affects the stability and chemiluminogenic ability of this group of compounds. Presenting as it does the crystal structure of chemiluminogen (I) and its precursor (II), this paper extends, together with our earlier publications on the crystallography of phenyl acridine-9-carboxylates (Meszko et al., 2002; Sikorski et al., 2005), the range of chemiluminogens with potentially interesting applications.
With respective average deviations from planarity of 0.0077 and 0.0094 Å, the acridine and phenyl moieties in (I) are oriented at an angle of 33.4 (2)° (defined as δ, the angle between the mean planes delineated by all the non-H atoms of the acridine and phenyl moieties; Fig. 1, Table 1). The carboxyl group is twisted at an angle of 62.0 (2)° relative to the acridine skeleton (defined as ε, the angle between the mean planes delineated by all the non-H atoms of the acridine moiety and atoms C15, O16 and O17). The H atoms of the methyl group occupy two orientations, rotated by 60° with respect to one another, each with an occupancy of 0.5.
In the crystalline phase, adjacent cations of (I) are oriented either parallel or anti-parallel. In the latter case, they are related by a centre of symmetry (Fig. 2). Antiparallel-oriented cations of (I), together with CF3SO3− anions, form layers in which the molecules are linked via a network of C—H···O interactions involving H atoms from the acridine moiety (at C7) or H atoms from the phenyl moiety (at C20), and two of the O atoms of the CF3SO3− anion (Fig. 2, Table 2), as well as π–π interactions between phenyl rings (Fig. 2, Table 3). These layers are linked via a network of multidirectional π–π interactions between acridine rings (Fig. 2, Table 3). The whole lattice is stabilized by electrostatic interactions between the ions.
With respective average deviations from planarity of 0.0107 and 0.0036 Å, the δ angle between the acridine and phenyl moieties in (II) is 9.3 (2)° (Fig. 3, Table 4). The carboxyl group is twisted at an ε angle of 77.2 (2)° relative to the acridine skeleton.
Adjacent molecules of (II) are oriented either parallel or antiparallel. In the latter case, they are related by a centre of symmetry. Parallel-oriented molecules are arranged in chains stabilized via C—H···Cl interactions involving one of the H atoms of the acridine moiety (at C7) and one of the Cl atoms (Cl25) (Fig. 4, Table 5). Oriented either parallel or antiparallel (Fig. 4), these chains are stabilized, in the latter case, via multidirectional π–π interactions involving the acridine and phenyl moieties (Fig. 4, Table 6), and generally via dispersive interactions.