9-(2,6-Dichloro­phen­oxycarbonyl)-10-methyl­acridinium trifluoro­methane­sulfonate and its precursor 2,6-dichloro­phenyl acridine-9-carboxyl­ate

The title compounds, C₂₁H₁₄Cl₂NO₂⁺·CF₃O₃S⁻, (I), and C₂₀H₁₁Cl₂NO₂, (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 CF₃SO₃⁻ 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).

S1. Comment

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.

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.2U_eq(C).

Computing details

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).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and 25% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The arrangement of the ions of (I) in the unit cell, viewed along the a axis. The C—H···O interactions are represented by dashed lines [symmetry code: (i) −1 + x, y, z] and the π–π interactions by dotted lines [symmetry codes: (ii) −x, 1 − y, −z; (iii) −x, 2 − y, 1 − z]. H atoms not involved in C—H···O interactions have been omitted.
	Fig. 3. The molecular structure of (II), showing the atom-labelling scheme and 25% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The arrangement of the molecules of (II) in the unit cell, viewed along the a axis. The C—H···Cl interactions are represented by dashed lines [symmetry code: (i) 1 + x, 1 + y, z], the π–π interactions by dotted lines [symmetry codes: (ii) 2 − x, 1 − y, 2 − z; (iii) 1 − x, 1 − y, 1 − z]. H atoms not involved in C—H···Cl interactions have been removed.

(I) 9-[2,6-Dichlorophenoxy)carbonyl]-10-methylacridinium trifluoromethanesulfonate

Crystal data

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) Å^3

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.052P)^2 + 0.5298P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0037 (1)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O30^i	0.93	2.52	3.404 (5)	160

Symmetry code: (i) x−1, y, z.

(II) 2,6-dichlorophenyl acridine-9-carboxylate

Crystal data

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) Å^3

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 0.1815P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (2)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cl25^i	0.93	2.83	3.570 (3)	137

Symmetry code: (i) x+1, y+1, z.