Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027145/er6021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027145/er6021Isup2.hkl |
CCDC reference: 287554
The title compound was synthesized by heating commercially available acridine-9-carboxylic acid with excess thionyl chloride. The product of this reaction, the acid chloride, was reacted with 2,6-dibromophenol (Sato, 1996). The synthesis was carried out in dichloromethane in the presence of triethylamine and catalytic amounts of 4-dimethylaminopyridine. [Please give quantities of reagents, reaction conditions etc.] The crude product was purified chromatographically (SiO2, n-hexane/ethyl acetate, 3:2 v/v). Yellow crystals suitable for X-ray analysis were grown from cyclohexane (m.p. 428–429 K).
All 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).
Data collection: KM-4 Software (Kuma, 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).
C20H11Br2NO2 | Z = 2 |
Mr = 457.12 | F(000) = 448 |
Triclinic, P1 | Dx = 1.813 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.385 (2) Å | Cell parameters from 50 reflections |
b = 9.840 (2) Å | θ = 2.5–25.0° |
c = 11.246 (2) Å | µ = 4.85 mm−1 |
α = 66.22 (3)° | T = 290 K |
β = 77.23 (3)° | Prism, yellow |
γ = 61.85 (3)° | 0.5 × 0.4 × 0.3 mm |
V = 837.4 (4) Å3 |
Kuma KM-4 diffractometer | 1803 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = −10→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.112, Tmax = 0.233 | l = 0→13 |
3074 measured reflections | 3 standard reflections every 200 reflections |
2909 independent reflections | intensity decay: 0.4% |
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)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0616P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.85 | (Δ/σ)max < 0.001 |
2909 reflections | Δρmax = 0.36 e Å−3 |
227 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0039 (11) |
C20H11Br2NO2 | γ = 61.85 (3)° |
Mr = 457.12 | V = 837.4 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.385 (2) Å | Mo Kα radiation |
b = 9.840 (2) Å | µ = 4.85 mm−1 |
c = 11.246 (2) Å | T = 290 K |
α = 66.22 (3)° | 0.5 × 0.4 × 0.3 mm |
β = 77.23 (3)° |
Kuma KM-4 diffractometer | 1803 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.112, Tmax = 0.233 | 3 standard reflections every 200 reflections |
3074 measured reflections | intensity decay: 0.4% |
2909 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.36 e Å−3 |
2909 reflections | Δρmin = −0.33 e Å−3 |
227 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8165 (4) | 0.3693 (4) | 0.0252 (3) | 0.0446 (9) | |
H1 | 0.7268 | 0.3676 | 0.0801 | 0.054* | |
C2 | 0.8062 (5) | 0.5101 (4) | −0.0703 (3) | 0.0516 (10) | |
H2 | 0.7091 | 0.6041 | −0.0805 | 0.062* | |
C3 | 0.9382 (5) | 0.5188 (5) | −0.1551 (4) | 0.0548 (10) | |
H3 | 0.9287 | 0.6181 | −0.2198 | 0.066* | |
C4 | 1.0791 (5) | 0.3830 (5) | −0.1428 (3) | 0.0494 (10) | |
H4 | 1.1658 | 0.3890 | −0.2003 | 0.059* | |
C5 | 1.4138 (4) | −0.1775 (5) | 0.0639 (4) | 0.0505 (10) | |
H5 | 1.4971 | −0.1622 | 0.0061 | 0.061* | |
C6 | 1.4402 (4) | −0.3276 (5) | 0.1523 (4) | 0.0527 (10) | |
H6 | 1.5416 | −0.4150 | 0.1556 | 0.063* | |
C7 | 1.3136 (5) | −0.3527 (4) | 0.2406 (4) | 0.0499 (9) | |
H7 | 1.3321 | −0.4577 | 0.2992 | 0.060* | |
C8 | 1.1682 (4) | −0.2281 (4) | 0.2408 (3) | 0.0406 (8) | |
H8 | 1.0881 | −0.2474 | 0.3009 | 0.049* | |
C9 | 0.9866 (4) | 0.0716 (4) | 0.1431 (3) | 0.0339 (7) | |
N10 | 1.2415 (3) | 0.1024 (4) | −0.0353 (3) | 0.0439 (7) | |
C11 | 0.9627 (4) | 0.2226 (4) | 0.0439 (3) | 0.0356 (7) | |
C12 | 1.0968 (4) | 0.2310 (4) | −0.0432 (3) | 0.0394 (8) | |
C13 | 1.1341 (4) | −0.0655 (4) | 0.1502 (3) | 0.0351 (7) | |
C14 | 1.2605 (4) | −0.0425 (4) | 0.0579 (3) | 0.0401 (8) | |
C15 | 0.8517 (4) | 0.0640 (4) | 0.2410 (3) | 0.0351 (8) | |
O16 | 0.9044 (3) | −0.0041 (3) | 0.3649 (2) | 0.0374 (5) | |
O17 | 0.7146 (3) | 0.1154 (3) | 0.2191 (2) | 0.0531 (7) | |
C18 | 0.7849 (4) | 0.0068 (4) | 0.4638 (3) | 0.0346 (8) | |
C19 | 0.7399 (4) | −0.1203 (4) | 0.5313 (3) | 0.0358 (8) | |
C20 | 0.6281 (4) | −0.1116 (5) | 0.6333 (3) | 0.0435 (9) | |
H20 | 0.5984 | −0.1976 | 0.6781 | 0.052* | |
C21 | 0.5603 (4) | 0.0257 (5) | 0.6688 (3) | 0.0469 (9) | |
H21 | 0.4860 | 0.0311 | 0.7388 | 0.056* | |
C22 | 0.6012 (4) | 0.1542 (5) | 0.6020 (3) | 0.0448 (9) | |
H22 | 0.5537 | 0.2473 | 0.6254 | 0.054* | |
C23 | 0.7139 (4) | 0.1443 (4) | 0.4992 (3) | 0.0395 (8) | |
Br24 | 0.83211 (5) | −0.30774 (4) | 0.48304 (4) | 0.05415 (16) | |
Br25 | 0.77029 (5) | 0.32050 (5) | 0.40609 (4) | 0.05659 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.050 (2) | 0.046 (2) | 0.034 (2) | −0.0199 (18) | 0.0022 (17) | −0.0136 (18) |
C2 | 0.058 (3) | 0.046 (2) | 0.041 (2) | −0.0160 (19) | −0.0039 (18) | −0.0119 (18) |
C3 | 0.077 (3) | 0.047 (2) | 0.038 (2) | −0.034 (2) | −0.007 (2) | −0.0006 (17) |
C4 | 0.060 (3) | 0.060 (2) | 0.034 (2) | −0.040 (2) | 0.0031 (17) | −0.0074 (18) |
C5 | 0.042 (2) | 0.059 (2) | 0.051 (2) | −0.0230 (19) | 0.0138 (17) | −0.027 (2) |
C6 | 0.042 (2) | 0.054 (2) | 0.053 (2) | −0.0101 (18) | 0.0038 (18) | −0.025 (2) |
C7 | 0.057 (2) | 0.040 (2) | 0.047 (2) | −0.0196 (19) | 0.0026 (18) | −0.0138 (17) |
C8 | 0.048 (2) | 0.0409 (19) | 0.0343 (19) | −0.0229 (17) | 0.0062 (16) | −0.0142 (15) |
C9 | 0.0397 (19) | 0.0426 (19) | 0.0259 (17) | −0.0243 (16) | 0.0028 (14) | −0.0121 (15) |
N10 | 0.0405 (17) | 0.0547 (19) | 0.0351 (17) | −0.0257 (15) | 0.0100 (13) | −0.0138 (15) |
C11 | 0.0426 (18) | 0.0445 (19) | 0.0254 (16) | −0.0234 (15) | 0.0012 (14) | −0.0133 (15) |
C12 | 0.050 (2) | 0.052 (2) | 0.0263 (17) | −0.0332 (18) | 0.0040 (15) | −0.0120 (16) |
C13 | 0.0389 (19) | 0.0427 (19) | 0.0299 (18) | −0.0221 (16) | 0.0019 (14) | −0.0145 (15) |
C14 | 0.0379 (19) | 0.053 (2) | 0.038 (2) | −0.0246 (17) | 0.0065 (15) | −0.0223 (18) |
C15 | 0.040 (2) | 0.0394 (18) | 0.0269 (18) | −0.0209 (16) | 0.0024 (14) | −0.0096 (14) |
O16 | 0.0305 (12) | 0.0459 (13) | 0.0282 (12) | −0.0157 (10) | 0.0055 (10) | −0.0101 (10) |
O17 | 0.0420 (15) | 0.0836 (19) | 0.0352 (14) | −0.0363 (14) | 0.0005 (11) | −0.0119 (13) |
C18 | 0.0318 (18) | 0.0436 (19) | 0.0254 (18) | −0.0166 (15) | 0.0010 (14) | −0.0098 (15) |
C19 | 0.0327 (18) | 0.0369 (18) | 0.0301 (18) | −0.0133 (14) | −0.0044 (14) | −0.0047 (14) |
C20 | 0.039 (2) | 0.052 (2) | 0.0326 (19) | −0.0252 (17) | 0.0038 (15) | −0.0046 (16) |
C21 | 0.038 (2) | 0.068 (3) | 0.0320 (19) | −0.0246 (19) | 0.0077 (16) | −0.0171 (18) |
C22 | 0.042 (2) | 0.056 (2) | 0.040 (2) | −0.0206 (17) | 0.0058 (16) | −0.0256 (18) |
C23 | 0.0421 (19) | 0.0445 (19) | 0.0320 (18) | −0.0239 (16) | 0.0039 (15) | −0.0098 (15) |
Br24 | 0.0545 (3) | 0.0409 (2) | 0.0616 (3) | −0.02163 (18) | 0.00636 (19) | −0.01567 (18) |
Br25 | 0.0730 (3) | 0.0515 (2) | 0.0502 (3) | −0.0379 (2) | 0.0072 (2) | −0.01362 (19) |
C1—C2 | 1.343 (5) | C9—C15 | 1.493 (4) |
C1—C11 | 1.422 (5) | N10—C12 | 1.339 (5) |
C1—H1 | 0.9300 | N10—C14 | 1.342 (4) |
C2—C3 | 1.402 (5) | C11—C12 | 1.428 (5) |
C2—H2 | 0.9300 | C13—C14 | 1.433 (4) |
C3—C4 | 1.348 (5) | C15—O16 | 1.369 (4) |
C3—H3 | 0.9300 | C15—O17 | 1.182 (4) |
C4—C12 | 1.420 (5) | O16—C18 | 1.393 (3) |
C4—H4 | 0.9300 | C18—C23 | 1.378 (5) |
C5—C6 | 1.345 (5) | C18—C19 | 1.382 (5) |
C5—C14 | 1.416 (5) | C19—C20 | 1.373 (4) |
C5—H5 | 0.9300 | C19—Br24 | 1.881 (3) |
C6—C7 | 1.420 (5) | C20—C21 | 1.379 (5) |
C6—H6 | 0.9300 | C20—H20 | 0.9300 |
C7—C8 | 1.336 (5) | C21—C22 | 1.369 (5) |
C7—H7 | 0.9300 | C21—H21 | 0.9300 |
C8—C13 | 1.431 (5) | C22—C23 | 1.385 (4) |
C8—H8 | 0.9300 | C22—H22 | 0.9300 |
C9—C13 | 1.394 (5) | C23—Br25 | 1.882 (3) |
C9—C11 | 1.401 (5) | ||
C2—C1—C11 | 121.0 (3) | N10—C12—C4 | 117.4 (3) |
C2—C1—H1 | 119.5 | N10—C12—C11 | 123.4 (3) |
C11—C1—H1 | 119.5 | C4—C12—C11 | 119.2 (3) |
C1—C2—C3 | 121.6 (4) | C9—C13—C8 | 125.1 (3) |
C1—C2—H2 | 119.2 | C9—C13—C14 | 117.5 (3) |
C3—C2—H2 | 119.2 | C8—C13—C14 | 117.4 (3) |
C4—C3—C2 | 119.9 (3) | N10—C14—C5 | 117.5 (3) |
C4—C3—H3 | 120.0 | N10—C14—C13 | 123.1 (3) |
C2—C3—H3 | 120.0 | C5—C14—C13 | 119.4 (3) |
C3—C4—C12 | 120.8 (3) | C9—C15—O16 | 111.0 (3) |
C3—C4—H4 | 119.6 | C9—C15—O17 | 126.6 (3) |
C12—C4—H4 | 119.6 | C15—O16—C18 | 116.1 (2) |
C6—C5—C14 | 120.8 (3) | O16—C15—O17 | 122.4 (3) |
C6—C5—H5 | 119.6 | C23—C18—C19 | 118.9 (3) |
C14—C5—H5 | 119.6 | C23—C18—O16 | 119.6 (3) |
C5—C6—C7 | 120.1 (3) | C19—C18—O16 | 121.4 (3) |
C5—C6—H6 | 119.9 | C20—C19—C18 | 120.8 (3) |
C7—C6—H6 | 119.9 | C20—C19—Br24 | 119.4 (3) |
C8—C7—C6 | 121.2 (3) | C18—C19—Br24 | 119.8 (2) |
C8—C7—H7 | 119.4 | C19—C20—C21 | 119.5 (3) |
C6—C7—H7 | 119.4 | C19—C20—H20 | 120.2 |
C7—C8—C13 | 121.0 (3) | C21—C20—H20 | 120.2 |
C7—C8—H8 | 119.5 | C22—C21—C20 | 120.7 (3) |
C13—C8—H8 | 119.5 | C22—C21—H21 | 119.7 |
C13—C9—C11 | 120.2 (3) | C20—C21—H21 | 119.7 |
C13—C9—C15 | 121.7 (3) | C21—C22—C23 | 119.4 (3) |
C11—C9—C15 | 118.1 (3) | C21—C22—H22 | 120.3 |
C12—N10—C14 | 118.3 (3) | C23—C22—H22 | 120.3 |
C9—C11—C1 | 125.1 (3) | C18—C23—C22 | 120.7 (3) |
C9—C11—C12 | 117.4 (3) | C18—C23—Br25 | 119.5 (2) |
C1—C11—C12 | 117.5 (3) | C22—C23—Br25 | 119.8 (3) |
C11—C1—C2—C3 | −0.2 (6) | C6—C5—C14—N10 | −178.0 (4) |
C1—C2—C3—C4 | 1.0 (6) | C6—C5—C14—C13 | 2.2 (6) |
C2—C3—C4—C12 | −1.2 (6) | C9—C13—C14—N10 | −1.5 (5) |
C14—C5—C6—C7 | 0.4 (6) | C8—C13—C14—N10 | 177.3 (3) |
C5—C6—C7—C8 | −2.3 (6) | C9—C13—C14—C5 | 178.2 (3) |
C6—C7—C8—C13 | 1.4 (6) | C8—C13—C14—C5 | −3.0 (5) |
C13—C9—C11—C1 | 178.5 (3) | C13—C9—C15—O17 | −132.9 (4) |
C15—C9—C11—C1 | −2.9 (5) | C15—O16—C18—C23 | −87.1 (4) |
C13—C9—C11—C12 | −3.2 (5) | C13—C9—C15—O16 | 50.6 (4) |
C15—C9—C11—C12 | 175.4 (3) | C11—C9—C15—O16 | −128.1 (3) |
C2—C1—C11—C9 | 177.9 (4) | O17—C15—O16—C18 | −6.9 (5) |
C2—C1—C11—C12 | −0.4 (5) | C9—C15—O16—C18 | 169.8 (3) |
C14—N10—C12—C4 | −179.7 (3) | C11—C9—C15—O17 | 48.4 (5) |
C14—N10—C12—C11 | 1.3 (5) | C15—O16—C18—C19 | 95.5 (3) |
C3—C4—C12—N10 | −178.5 (3) | C23—C18—C19—C20 | −1.0 (5) |
C3—C4—C12—C11 | 0.6 (5) | O16—C18—C19—C20 | 176.5 (3) |
C9—C11—C12—N10 | 0.8 (5) | C23—C18—C19—Br24 | 178.9 (2) |
C1—C11—C12—N10 | 179.2 (3) | O16—C18—C19—Br24 | −3.6 (4) |
C9—C11—C12—C4 | −178.2 (3) | C18—C19—C20—C21 | −0.1 (5) |
C1—C11—C12—C4 | 0.2 (5) | Br24—C19—C20—C21 | −180.0 (3) |
C11—C9—C13—C8 | −175.1 (3) | C19—C20—C21—C22 | 1.1 (5) |
C15—C9—C13—C8 | 6.3 (5) | C20—C21—C22—C23 | −1.1 (5) |
C11—C9—C13—C14 | 3.6 (5) | C19—C18—C23—C22 | 1.0 (5) |
C15—C9—C13—C14 | −175.1 (3) | O16—C18—C23—C22 | −176.5 (3) |
C7—C8—C13—C9 | 179.9 (3) | C19—C18—C23—Br25 | −178.6 (2) |
C7—C8—C13—C14 | 1.3 (5) | O16—C18—C23—Br25 | 3.9 (4) |
C12—N10—C14—C5 | 179.4 (3) | C21—C22—C23—C18 | 0.0 (5) |
C12—N10—C14—C13 | −0.9 (5) | C21—C22—C23—Br25 | 179.7 (3) |
Experimental details
Crystal data | |
Chemical formula | C20H11Br2NO2 |
Mr | 457.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 290 |
a, b, c (Å) | 9.385 (2), 9.840 (2), 11.246 (2) |
α, β, γ (°) | 66.22 (3), 77.23 (3), 61.85 (3) |
V (Å3) | 837.4 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.85 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Kuma KM-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.112, 0.233 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3074, 2909, 1803 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.081, 0.85 |
No. of reflections | 2909 |
No. of parameters | 227 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.33 |
Computer programs: KM-4 Software (Kuma, 1989), KM-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97 and PLATON (Spek, 2003).
C9—C11 | 1.401 (5) | C15—O17 | 1.182 (4) |
C9—C15 | 1.493 (4) | O16—C18 | 1.393 (3) |
N10—C12 | 1.339 (5) | C18—C19 | 1.382 (5) |
C15—O16 | 1.369 (4) | C19—Br24 | 1.881 (3) |
C9—C15—O16 | 111.0 (3) | C15—O16—C18 | 116.1 (2) |
C9—C15—O17 | 126.6 (3) | O16—C15—O17 | 122.4 (3) |
C9—C15—O16—C18 | 169.8 (3) | C15—O16—C18—C19 | 95.5 (3) |
C11—C9—C15—O17 | 48.4 (5) | O16—C18—C19—Br24 | −3.6 (4) |
CgI | CgJ | Cg···Cg | Dihedral angle | Interplanar dist. | Offset |
1 | 1i | 3.880 (2) | 0.0 | 3.590 (3) | 1.472 (2) |
2 | 2ii | 3.766 (2) | 0.0 | 3.491 (3) | 1.413 (2) |
2 | 3i | 3.890 (2) | 2.0 | 3.479 (3) | 1.740 (2) |
3 | 2i | 3.890 (2) | 2.0 | 3.530 (3) | 1.634 (2) |
Symmetry codes: (i) 2 − x, 1 − y, −z; (ii) 2 − x, −y, −z. Notes: Cg represents the centre of gravity of the rings, as follows: Cg1, ring C9/C11/C12/N10/C14/C13; Cg2, ring C1/C2/C3/C4/C12/C11; Cg3, ring C5/C6/C7/C8/C13/C14. Cg···Cg is the distance between ring centroids. The dihedral angle is that between the planes of CgI and CgJ. The interplanar distance is the perpendicular distance of CgI from ring J. Offset is the perpendicular distance of ring I from ring J. |
Phenyl acridine-9-carboxylates have become interesting chemiluminescent agents, since they can be oxidized by H2O2, persulfates, peroxides or other oxidants to electronically excited 9-acridinones (Dodeigne et al., 2000; Razawi & McCapra, 2000), which are known to be efficient light emitters (Boużyk et al., 2003). For this reason, these compounds are widely applied as chemiluminescent indicators, or fragments of chemiluminescent labels, in immunological, medical, environmental and biochemical analyses (Dodeigne et al., 2000). Continuing the search for new, analytically useful chemiluminogens, we synthesized dibromophenyl acridine-9-carboxylate in order to find out how the presence of the Br atoms affects the stability and chemiluminogenic properties of this group of compounds. This paper, together with our earlier publications on the crystallography of phenyl acridine-9-carboxylates (Meszko et al., 2002; Sikorski et al., 2005a,b), thus extends the prospects of finding further chemiluminogens with interesting practical applications.
Bond lengths and angles may be regarded as typical for acridine-based derivatives (Table 1).
The acridine and phenyl groups are planar, with average deviations of 0.012 (3) and 0.005 (3) Å, respectively. The least-squares planes (defined by all non-H atoms) of the acridine and phenyl groups are inclined at an angle of 41.2 (2)° to each other (Fig. 1).
The angle between the least-squares planes of the acridine group and the carboxyl group, defined by atoms C16, O16 and O17, is 51.0 (3)°. Adjacent molecules are oriented either parallel or antiparallel. In the latter case, there are four intermolecular π–π interactions involving the acridine rings (Fig. 2 and Table 2). In addition, there is a short intermolecular Br···Br contact [Br24···Br24(2 − x, −1 − y, 1 − z) = 3.54 (1) Å].