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Acta Cryst. (2010). E66, o1313-o1314    [ doi:10.1107/S1600536810016296 ]

9-(4-Bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

D. Trzybinski, K. Krzyminski, A. Sikorski and J. Blazejowski

Abstract top

In the crystal structure of the title compound, C21H15BrNO2+·CF3SO3-, the cations form inversion dimers through [pi]-[pi] interactions between the acridine ring systems. These dimers are further linked by C-H...[pi] and C-Br...[pi] interactions. The cations and anions are connected by multidirectional C-H...O and C-F...[pi] interactions. The acridine and benzene ring systems are oriented at 10.8 (1)°. The carboxyl group is twisted at an angle of 85.2 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine units are parallel or almost parallel [inclined at an angle of 1.4 (1)°] in the crystal structure.

Comment top

The cations of 9-(phenoxycarbonyl)-10-methylacridinium salts react efficiently with H2O2 in alkaline media producing light (Zomer & Jacquemijns, 2001; Adamczyk & Mattingly, 2002). This effect means that the compounds can serve as chemiluminescent indicators or as chemiluminogenic fragments of chemiluminescent labels in assays of biologically and environmentally important entities such as antigens, antibodies, enzymes or DNA fragments (Zomer & Jacquemijns, 2001; Adamczyk & Mattingly, 2002; Roda et al. , 2003; King et al., 2007). The chemiluminogenic features of the compounds depend on the structure of the cations, particularly the phenoxycarbonyl fragment which is removed during their oxidation leading to electronically excited 10-methyl-9-acridinone molecules (Rak et al., 1999; Zomer & Jacquemijns, 2001). It has been found that the efficiency of chemiluminescence – crucial for analytical applications – is influenced by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). This prompted us to synthesize and investigate derivatives substituted in this latter fragment. In this paper, a continuation of a series on bromo-substituted derivatives (Sikorski et al., 2005a), we present the structure of the title compound.

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., 2005a,b). With respective average deviations from planarity of 0.0442 (3) Å and 0.0046 (3) Å, the acridine and benzene ring systems are oriented at 10.8 (1)°. The carboxyl group is twisted at an angle of 85.2 (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 almost parallel (remain at an angle of 1.4 (1)°) in the lattice.

In the crystal structure, the inversely oriented cations form dimers through π–π interactions involving acridine moieties (Table 3, Fig. 2). These dimers are further linked by C–H···π (Table 1, Fig. 2) and C–Br···π (Table 2, Fig. 2) interactions. The cations and anions are connected by multidirectional C–H···O (Table 1, Fig. 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 C–Br···π interactions have been reported by others (Seo et al., 2009). The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.

Related literature top

For background to the chemiluminogenic properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: Adamczyk & Mattingly (2002); King et al. (2007); Rak et al. (1999); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2005a,b). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006); Seo et al. (2009); Takahashi et al. (2001). For the synthesis, see: Sato (1996); Sikorski et al. (2005a,b).

Experimental top

The title compound was obtained by treating 4-bromophenyl acridine-9-carboxylate [synthesized by heating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride and reacting the product thus obtained with an equimolar amount of 4-bromophenol (Sato, 1996; Sikorski et al., 2005b)] with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in dichloromethane (Sikorski et al., 2005a). The crude 9-(4-bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with a 25 v/v excess of diethyl ether. Yellow crystals suitable for X-ray investigations were grown from anhydrous ethanol (m.p. 504 - 505 K).

Refinement top

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.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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).

Figures top
[Figure 1] 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 bond is represented by a dashed line.
[Figure 2] 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, C–Br–π and π–π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) –x + 1, y – 1/2, –z + 1/2; (ii) –x, y – 1/2, –z + 1/2; (iii) x – 1, y, z; (iv) x + 1, y, z; (v) x, –y + 3/2, z – 1/2; (vi) –x, –y + 1, –z.]
9-(4-Bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate top
Crystal data top
C21H15BrNO2+·CF3O3S−F(000) = 1088
Mr = 542.32Dx = 1.628 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 14728 reflections
a = 9.5755 (2) Åθ = 3.0–29.2°
b = 20.4912 (7) ŵ = 2.01 mm−1
c = 11.6241 (5) ÅT = 295 K
β = 104.011 (3)°Plate, yellow
V = 2212.95 (13) Å30.37 × 0.15 × 0.05 mm
Z = 4
Data collection top
Oxford Diffraction Gemini R Ultra Ruby CCD
diffractometer		3910 independent reflections
Radiation source: enhanced (Mo) X-ray Source2200 reflections with I > 2σ(I)
graphiteRint = 0.048
Detector resolution: 10.4002 pixels mm-1θmax = 25.1°, θmin = 3.0°
ω scansh = −11→11
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		k = −24→24
Tmin = 0.77, Tmax = 0.92l = −13→13
50472 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.0642P)2]
where P = (Fo2 + 2Fc2)/3
3910 reflections(Δ/σ)max = 0.001
299 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
C21H15BrNO2+·CF3O3S−V = 2212.95 (13) Å3
Mr = 542.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.5755 (2) ŵ = 2.01 mm−1
b = 20.4912 (7) ÅT = 295 K
c = 11.6241 (5) Å0.37 × 0.15 × 0.05 mm
β = 104.011 (3)°
Data collection top
Oxford Diffraction Gemini R Ultra Ruby CCD
diffractometer		3910 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		2200 reflections with I > 2σ(I)
Tmin = 0.77, Tmax = 0.92Rint = 0.048
50472 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.56 e Å−3
S = 0.98Δρmin = −0.62 e Å−3
3910 reflectionsAbsolute structure: ?
299 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.1494 (3)0.43387 (19)0.1754 (3)0.0703 (10)
H10.24930.43590.19100.084*
C20.0842 (4)0.3755 (2)0.1601 (4)0.0794 (11)
H20.13870.33760.16420.095*
C3−0.0654 (4)0.3715 (2)0.1382 (3)0.0787 (11)
H3−0.10920.33070.12830.094*
C4−0.1483 (3)0.4255 (2)0.1309 (3)0.0684 (10)
H4−0.24770.42130.11710.082*
C5−0.1859 (4)0.6625 (2)0.1220 (3)0.0773 (11)
H5−0.28580.65990.10220.093*
C6−0.1200 (4)0.7217 (2)0.1332 (4)0.0902 (12)
H6−0.17660.75910.12050.108*
C70.0303 (4)0.7284 (2)0.1631 (4)0.0896 (12)
H70.07250.76960.17080.108*
C80.1126 (4)0.67394 (19)0.1808 (3)0.0734 (10)
H80.21230.67810.20090.088*
C90.1328 (3)0.55402 (17)0.1829 (3)0.0544 (8)
N10−0.1650 (2)0.54462 (15)0.1304 (2)0.0582 (7)
C110.0688 (3)0.49303 (17)0.1682 (3)0.0574 (9)
C12−0.0853 (3)0.48819 (17)0.1439 (3)0.0553 (8)
C130.0508 (3)0.61081 (17)0.1694 (3)0.0601 (9)
C14−0.1030 (3)0.60523 (18)0.1404 (3)0.0596 (9)
C150.2939 (3)0.56004 (16)0.2072 (3)0.0573 (8)
O160.35203 (19)0.56616 (11)0.32302 (19)0.0620 (6)
O170.3586 (2)0.55888 (15)0.1321 (2)0.0855 (8)
C180.5032 (3)0.57634 (17)0.3564 (3)0.0521 (8)
C190.5556 (3)0.63811 (17)0.3571 (3)0.0606 (9)
H190.49340.67300.33320.073*
C200.7017 (3)0.64830 (17)0.3934 (3)0.0647 (9)
H200.73960.69010.39330.078*
C210.7905 (3)0.59614 (18)0.4296 (3)0.0639 (9)
C220.7375 (4)0.5340 (2)0.4306 (3)0.0796 (11)
H220.79950.49920.45660.095*
C230.5906 (4)0.52369 (18)0.3924 (3)0.0713 (10)
H230.55220.48190.39130.086*
Br240.99257 (4)0.61111 (2)0.48030 (5)0.1038 (2)
C25−0.3252 (3)0.5406 (2)0.1034 (3)0.0775 (11)
H25A−0.36090.57160.15110.116*
H25B−0.35330.49740.12050.116*
H25C−0.36440.55010.02100.116*
S260.47869 (9)0.82754 (4)0.30872 (9)0.0676 (3)
O270.6132 (3)0.79768 (13)0.3588 (3)0.0980 (9)
O280.4780 (3)0.89700 (12)0.3260 (3)0.1005 (9)
O290.3556 (3)0.79269 (14)0.3249 (3)0.1026 (9)
C300.4620 (5)0.8203 (3)0.1534 (4)0.1024 (14)
F310.5746 (4)0.8502 (2)0.1247 (3)0.1619 (13)
F320.4639 (4)0.75825 (19)0.1220 (3)0.1721 (14)
F330.3479 (4)0.8468 (2)0.0881 (3)0.1719 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0475 (17)0.081 (3)0.084 (3)0.0049 (19)0.0198 (16)0.009 (2)
C20.066 (2)0.077 (3)0.098 (3)0.009 (2)0.025 (2)0.010 (2)
C30.068 (2)0.074 (3)0.094 (3)−0.007 (2)0.019 (2)0.005 (2)
C40.0476 (17)0.095 (3)0.065 (2)−0.013 (2)0.0176 (15)0.004 (2)
C50.053 (2)0.092 (3)0.086 (3)0.016 (2)0.0137 (18)0.001 (2)
C60.077 (3)0.082 (3)0.108 (3)0.027 (2)0.016 (2)0.007 (3)
C70.073 (2)0.074 (3)0.121 (3)0.004 (2)0.023 (2)0.002 (2)
C80.0522 (18)0.075 (3)0.093 (3)−0.0007 (19)0.0168 (17)0.001 (2)
C90.0341 (14)0.074 (2)0.056 (2)0.0012 (15)0.0129 (13)−0.0011 (16)
N100.0343 (12)0.083 (2)0.0595 (17)0.0019 (14)0.0148 (11)−0.0024 (14)
C110.0371 (16)0.078 (3)0.059 (2)0.0031 (16)0.0150 (14)0.0038 (17)
C120.0378 (15)0.078 (3)0.051 (2)−0.0011 (16)0.0126 (13)0.0025 (16)
C130.0408 (16)0.077 (3)0.064 (2)−0.0013 (17)0.0166 (14)0.0001 (17)
C140.0418 (16)0.077 (3)0.060 (2)0.0079 (17)0.0122 (14)0.0007 (17)
C150.0400 (16)0.068 (2)0.065 (2)−0.0002 (14)0.0159 (17)0.0015 (17)
O160.0393 (10)0.0869 (17)0.0597 (15)−0.0019 (10)0.0119 (10)−0.0009 (12)
O170.0402 (12)0.157 (3)0.0613 (15)−0.0036 (13)0.0155 (11)−0.0026 (15)
C180.0389 (15)0.064 (2)0.0523 (19)0.0018 (15)0.0094 (13)−0.0004 (16)
C190.0491 (18)0.061 (2)0.069 (2)0.0097 (16)0.0088 (15)0.0051 (18)
C200.0501 (18)0.060 (2)0.079 (2)0.0022 (16)0.0066 (16)−0.0022 (18)
C210.0429 (16)0.072 (3)0.072 (2)0.0043 (16)0.0035 (15)−0.0055 (18)
C220.059 (2)0.067 (3)0.102 (3)0.0148 (19)−0.0019 (19)0.004 (2)
C230.060 (2)0.058 (2)0.092 (3)0.0033 (17)0.0100 (18)0.0055 (19)
Br240.0442 (2)0.1080 (4)0.1442 (5)0.00493 (19)−0.0065 (2)−0.0176 (3)
C250.0321 (15)0.104 (3)0.093 (3)0.0019 (17)0.0103 (15)−0.012 (2)
S260.0539 (5)0.0615 (6)0.0876 (7)0.0009 (4)0.0176 (4)0.0017 (5)
O270.0639 (14)0.086 (2)0.130 (2)0.0090 (13)−0.0052 (14)0.0217 (16)
O280.0918 (18)0.0651 (19)0.150 (3)−0.0001 (13)0.0394 (18)−0.0211 (16)
O290.0775 (16)0.098 (2)0.144 (3)−0.0196 (14)0.0486 (16)0.0098 (18)
C300.104 (3)0.100 (4)0.102 (4)−0.001 (3)0.020 (3)−0.001 (3)
F310.162 (3)0.227 (4)0.115 (2)−0.019 (3)0.069 (2)0.029 (2)
F320.250 (4)0.141 (3)0.120 (2)0.006 (3)0.034 (2)−0.052 (2)
F330.139 (3)0.201 (4)0.134 (3)0.005 (2)−0.048 (2)0.047 (2)
Geometric parameters (Å, °) top
C1—C21.342 (5)C13—C141.433 (4)
C1—C111.429 (5)C15—O171.187 (4)
C1—H10.9300C15—O161.332 (4)
C2—C31.395 (5)O16—C181.421 (3)
C2—H20.9300C18—C191.361 (4)
C3—C41.352 (5)C18—C231.367 (4)
C3—H30.9300C19—C201.376 (4)
C4—C121.411 (5)C19—H190.9300
C4—H40.9300C20—C211.367 (5)
C5—C61.359 (5)C20—H200.9300
C5—C141.403 (5)C21—C221.372 (5)
C5—H50.9300C21—Br241.906 (3)
C6—C71.403 (5)C22—C231.385 (5)
C6—H60.9300C22—H220.9300
C7—C81.353 (5)C23—H230.9300
C7—H70.9300C25—H25A0.9600
C8—C131.415 (5)C25—H25B0.9600
C8—H80.9300C25—H25C0.9600
C9—C111.384 (4)S26—O271.418 (2)
C9—C131.391 (4)S26—O291.429 (2)
C9—C151.505 (4)S26—O281.438 (3)
N10—C141.369 (4)S26—C301.779 (5)
N10—C121.374 (4)C30—F331.290 (5)
N10—C251.491 (3)C30—F321.325 (5)
C11—C121.437 (4)C30—F311.350 (5)
C2—C1—C11121.5 (3)C5—C14—C13118.7 (3)
C2—C1—H1119.3O17—C15—O16125.5 (3)
C11—C1—H1119.3O17—C15—C9123.6 (3)
C1—C2—C3120.0 (4)O16—C15—C9110.8 (3)
C1—C2—H2120.0C15—O16—C18116.0 (2)
C3—C2—H2120.0C19—C18—C23122.3 (3)
C4—C3—C2121.7 (4)C19—C18—O16119.2 (3)
C4—C3—H3119.1C23—C18—O16118.4 (3)
C2—C3—H3119.1C18—C19—C20119.3 (3)
C3—C4—C12120.6 (3)C18—C19—H19120.4
C3—C4—H4119.7C20—C19—H19120.4
C12—C4—H4119.7C21—C20—C19119.1 (3)
C6—C5—C14120.0 (3)C21—C20—H20120.5
C6—C5—H5120.0C19—C20—H20120.5
C14—C5—H5120.0C20—C21—C22121.7 (3)
C5—C6—C7122.4 (4)C20—C21—Br24118.6 (3)
C5—C6—H6118.8C22—C21—Br24119.8 (2)
C7—C6—H6118.8C21—C22—C23119.2 (3)
C8—C7—C6118.8 (4)C21—C22—H22120.4
C8—C7—H7120.6C23—C22—H22120.4
C6—C7—H7120.6C18—C23—C22118.4 (3)
C7—C8—C13121.6 (3)C18—C23—H23120.8
C7—C8—H8119.2C22—C23—H23120.8
C13—C8—H8119.2N10—C25—H25A109.5
C11—C9—C13121.4 (3)N10—C25—H25B109.5
C11—C9—C15120.0 (3)H25A—C25—H25B109.5
C13—C9—C15118.5 (3)N10—C25—H25C109.5
C14—N10—C12122.4 (2)H25A—C25—H25C109.5
C14—N10—C25118.1 (3)H25B—C25—H25C109.5
C12—N10—C25119.5 (3)O27—S26—O29115.25 (18)
C9—C11—C1122.9 (3)O27—S26—O28113.86 (17)
C9—C11—C12119.3 (3)O29—S26—O28116.39 (17)
C1—C11—C12117.9 (3)O27—S26—C30103.3 (2)
N10—C12—C4122.8 (3)O29—S26—C30102.6 (2)
N10—C12—C11118.7 (3)O28—S26—C30102.8 (2)
C4—C12—C11118.4 (3)F33—C30—F32107.9 (4)
C9—C13—C8122.8 (3)F33—C30—F31106.0 (4)
C9—C13—C14118.6 (3)F32—C30—F31107.6 (5)
C8—C13—C14118.5 (3)F33—C30—S26114.7 (4)
N10—C14—C5121.8 (3)F32—C30—S26110.9 (4)
N10—C14—C13119.5 (3)F31—C30—S26109.4 (3)
C11—C1—C2—C3−0.8 (6)C6—C5—C14—C13−0.8 (5)
C1—C2—C3—C40.4 (6)C9—C13—C14—N102.0 (5)
C2—C3—C4—C120.8 (6)C8—C13—C14—N10−179.2 (3)
C14—C5—C6—C7−0.2 (6)C9—C13—C14—C5−177.4 (3)
C5—C6—C7—C80.5 (7)C8—C13—C14—C51.4 (5)
C6—C7—C8—C130.2 (6)C11—C9—C15—O1782.6 (4)
C13—C9—C11—C1176.7 (3)C13—C9—C15—O17−93.9 (4)
C15—C9—C11—C10.3 (5)C11—C9—C15—O16−96.8 (3)
C13—C9—C11—C12−2.9 (5)C13—C9—C15—O1686.6 (4)
C15—C9—C11—C12−179.4 (3)O17—C15—O16—C184.3 (5)
C2—C1—C11—C9−179.7 (3)C9—C15—O16—C18−176.2 (3)
C2—C1—C11—C12−0.1 (5)C15—O16—C18—C1985.8 (4)
C14—N10—C12—C4−178.4 (3)C15—O16—C18—C23−97.4 (3)
C25—N10—C12—C41.3 (4)C23—C18—C19—C201.0 (5)
C14—N10—C12—C11−0.6 (4)O16—C18—C19—C20177.7 (3)
C25—N10—C12—C11179.1 (3)C18—C19—C20—C21−1.0 (5)
C3—C4—C12—N10176.1 (3)C19—C20—C21—C220.0 (5)
C3—C4—C12—C11−1.7 (5)C19—C20—C21—Br24−179.7 (3)
C9—C11—C12—N103.0 (4)C20—C21—C22—C230.9 (6)
C1—C11—C12—N10−176.6 (3)Br24—C21—C22—C23−179.4 (3)
C9—C11—C12—C4−179.1 (3)C19—C18—C23—C22−0.1 (5)
C1—C11—C12—C41.3 (4)O16—C18—C23—C22−176.8 (3)
C11—C9—C13—C8−178.3 (3)C21—C22—C23—C18−0.9 (6)
C15—C9—C13—C8−1.8 (5)O27—S26—C30—F33−177.5 (4)
C11—C9—C13—C140.5 (5)O29—S26—C30—F3362.4 (4)
C15—C9—C13—C14176.9 (3)O28—S26—C30—F33−58.8 (4)
C7—C8—C13—C9177.7 (4)O27—S26—C30—F3260.0 (4)
C7—C8—C13—C14−1.1 (5)O29—S26—C30—F32−60.2 (4)
C12—N10—C14—C5177.5 (3)O28—S26—C30—F32178.7 (4)
C25—N10—C14—C5−2.2 (5)O27—S26—C30—F31−58.5 (4)
C12—N10—C14—C13−1.9 (5)O29—S26—C30—F31−178.6 (3)
C25—N10—C14—C13178.4 (3)O28—S26—C30—F3160.2 (4)
C6—C5—C14—N10179.8 (3)
Hydrogen-bond geometry (Å, °) top
Cg4 is the centroid of the C18–C23 ring.
D—H···AD—HH···AD···AD—H···A
C2—H2···O27i0.932.593.361 (5)141
C4—H4···O28ii0.932.503.365 (4)155
C20—H20···O270.932.503.176 (4)130
C25—H25A···Cg4iii0.962.813.569 (4)136
C25—H25B···O28ii0.962.533.472 (5)167
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
Cg4 is the centroid of the C18–C23 ring.
D—H···AD—HH···AD···AD—H···A
C2—H2···O27i0.932.593.361 (5)141
C4—H4···O28ii0.932.503.365 (4)155
C20—H20···O270.932.503.176 (4)130
C25—H25A···Cg4iii0.962.813.569 (4)136
C25—H25B···O28ii0.962.533.472 (5)167
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x−1, y, z.
Table 2
C–Br···π and C–F···π interactions (Å,°). top
XIJI···JX···JX–I···J
C21Br24Cg1iv3.958 (2)4.158 (3)82.3 (1)
C21Br24Cg3iv3.937 (2)4.235 (4)85.4 (2)
C30F31Cg4v3.212 (4)4.305 (5)137.5 (3)
Symmetry codes: (iv) x + 1, y, z; (v) x, –y + 3/2, z – 1/2.

Notes: Cg1, Cg3 and Cg4 are the centroids of the C9/N10/C11–C14, C5–C8/C13/C14 and C18–C23 rings, respectively.
Table 3
π–π interactions (Å,°). top
IJCgI···CgJDihedral angleCgI_PerpCgI_Offset
12vi3.650 (2)2.82 (16)3.623 (2)0.444 (2)
21vi3.650 (2)2.82 (16)3.623 (2)0.444 (2)
Symmetry code: (vi) –x, –y + 1, –z.

Notes: Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 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 top

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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