9-(2-Bromo­phen­oxy­carbon­yl)-10-methyl­acridinium trifluoro­methane­sulfonate

Trzybiński, D.; Sieradzan, A.; Krzymiński, K.; Błażejowski, J.

doi:10.1107/S1600536812020892

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1722-o1723

doi:10.1107/S1600536812020892

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9-(2-Bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate

Damian Trzybiński,^a Andrzej Sieradzan,^a Karol Krzymiński ^a and Jerzy Błażejowski ^a ^*

^aFaculty of Chemistry, University of Gdańsk, J. Sobieskiego 18, 80-952 Gdańsk, Poland
^*Correspondence e-mail: bla@chem.univ.gda.pl

(Received 19 April 2012; accepted 8 May 2012; online 16 May 2012)

In the crystal structure of the title compound, C₂₁H₁₅BrNO₂⁺·CF₃SO₃⁻, adjacent cations are linked through C—Br⋯π and π–π contacts [centroid–centroid distance = 3.744 (2) Å], and neighbouring cations and anions via C—H⋯O, C—F⋯π and S—O⋯π interactions. The acridine and benzene ring systems are oriented at a dihedral angle of 18.7 (1)°. The carboxy group is twisted at an angle of 69.3 (1)° relative to the acridine skeleton. The mean planes of adjacent acridine moieties are either parallel or inclined at an angle of 27.8 (1)° in the lattice.

Related literature

For general background to the chemiluminescent properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: King et al. (2007 ); Krzymiński et al. (2011 ); Roda et al. (2003 ); Zomer & Jacquemijns (2001 ). For related structures, see: Trzybiński et al. (2010 ). For intermolecular interactions, see: Dorn et al. (2005 ); Hunter et al. (2001 ); Novoa et al. (2006 ); Seo et al. (2009 ); Sikorski et al. (2005 ); Trzybiński et al. (2010). For similar C–Br⋯π, π–π, C–H⋯O, C–F⋯π and S–O⋯π interactions in related compounds, see: Sikorski et al. (2005); Trzybiński et al. (2010). For the synthesis, see: Sato (1996 ); Trzybiński et al. (2010).

Experimental

Crystal data

C₂₁H₁₅BrNO₂⁺·CF₃O₃S⁻
M_r = 542.32
Monoclinic, P 2₁ /c
a = 12.5718 (8) Å
b = 20.3617 (16) Å
c = 8.5162 (6) Å
β = 104.498 (7)°
V = 2110.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.11 mm⁻¹
T = 295 K
0.46 × 0.25 × 0.02 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.668, T_max = 1.000
16372 measured reflections
3735 independent reflections
2348 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.088
S = 0.92
3735 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O28ⁱ	0.93	2.54	3.289 (5)	137
C7—H7⋯O27	0.93	2.54	3.200 (5)	128
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
C—F⋯π, C—Br⋯π and S—O⋯π interactions (Å, °)

Cg1, Cg2 and Cg4 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C18–C23 rings, respectively.

X—I⋯J	I⋯J	X⋯J	X—I⋯J
C19—Br24⋯Cg4ⁱⁱ	3.523 (2)	4.847 (3)	124.6 (1)
C30—F32⋯Cg4ⁱⁱⁱ	3.648 (2)	4.310 (4)	110.8 (2)
S26—O27⋯Cg1^iv	3.821 (3)	3.708 (2)	74.8 (2)
S26—O28⋯Cg1^iv	3.414 (3)	3.708 (2)	90.3 (2)
S26—O28⋯Cg2^iv	3.358 (3)	4.445 (2)	132.2 (2)
Symmetry codes: (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z+2.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020892/fj2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020892/fj2548Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020892/fj2548Isup3.cml

checkCIF report

Comment top

The well-known chemiluminescence of 9-(phenoxycarbonyl)-10-methylacridinium salts has been utilized in chemiluminescent indicators and labels, which are commonly applied in assays of biologically and environmentally important entities (Zomer & Jacquemijns, 2001; Roda et al., 2003; King et al., 2007). The cations of these salts are oxidized by H₂O₂ in alkaline media, a reaction that is accompanied by the removal of the phenoxycarbonyl fragment and the conversion of the remaining part of the molecules to electronically excited, light-emitting 10-methyl-9-acridinone (Krzymiński et al., 2011). The efficiency of chemiluminescence – crucial for analytical applications – is affected by the constitution of the phenyl fragment (Zomer & Jacquemijns, 2001). In continuing our investigations on the latter aspect, we synthesized 9-(2-bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate, whose crystal structure is presented here.

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 (Trzybiński et al., 2010). With respective average deviations from planarity of 0.0519 (3) Å and 0.0034 (3) Å, the acridine and benzene ring systems are oriented at a dihedral angle of 18.7 (1)°. The carboxyl group is twisted at an angle of 69.3 (1)° relative to the acridine skeleton. The mean planes of the adjacent acridine moieties are parallel (remain at an angle of 0.0 (1)°) or inclined at an angle of 27.8 (1)° in the crystal.

The search for intermolecular interactions in the crystal using PLATON (Spek, 2009) has shown that the adjacent cations are linked by C–Br···π (Table 2, Fig. 2) and π-π (Table 3, Fig.2) contacts, and the cations and neighboring anions via C–H···O (Table 1, Figs. 1 and 2), C–F···π (Table 2, Fig. 2) and S–O···π (Table 2, Fig. 2) interactions. The C–H···O interactions are of the hydrogen bond type (Novoa et al. 2006). The C–F···π (Dorn et al., 2005), S–O···π (Dorn et al., 2005) and π–π (Hunter et al., 2001) interactions should be of an attractive nature. The C–Br···π interactions have been reported by others (Seo et al., 2009). We have found all the above interactions in many other 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates (e.g. Sikorski et al., 2005; Trzybiński et al., 2010). Mentioning them here is important in the context of the analysis and understanding of the crystal architecture of this group of compounds. 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 general background to the chemiluminescent properties of 9-phenoxycarbonyl-10-methylacridinium trifluoromethanesulfonates, see: King et al. (2007); Krzymiński et al. (2011); Roda et al. (2003); Zomer & Jacquemijns (2001). For related structures, see: Trzybiński et al. (2010). For intermolecular interactions, see: Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006); Seo et al. (2009); Sikorski et al. (2005); Trzybiński et al. (2010). For similar C–Br···π , π–π, C–H···O, C–F···π and S–O···π interactions in related compounds, see: Sikorski et al. (2005); Trzybiński et al. (2010). For the synthesis, see: Sato (1996); Trzybiński et al. (2010).

Experimental top

2-Bromophenylacridine-9-carboxylate was synthesized by esterification of 9-(chlorocarbonyl)acridine (obtained by treating acridine-9-carboxylic acid with a tenfold molar excess of thionyl chloride) with 2-bromophenol in anhydrous dichloromethane in the presence of N,N-diethylethanamine and a catalytic amount of N,N-dimethyl-4-pyridinamine (room temperature, 15h) (Sato, 1996). The product was purified chromatographically (SiO₂, cyclohexane/ethyl acetate, 1/1 v/v) and subsequently quaternarized with a fivefold molar excess of methyl trifluoromethanesulfonate dissolved in anhydrous dichloromethane (Trzybiński et al., 2010). The crude 9-(2-bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered and precipitated with a 20 v/v excess of diethyl ether. Light-orange crystals suitable for X-ray investigations were grown from methanol/water (2:1, v/v) solution (m.p. 495–497 K).

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

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.

Fig. 2. The arrangement of the ions in the crystal structure. The C–H···O interactions are represented by dashed lines, the C–F···π, C–Br···π, S–O···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 + 3/2; (ii) x, –y + 3/2, z – 1/2; (iii) –x, –y + 1, –z + 1; (iv) –x + 1, –y + 1, –z + 2; (v) –x + 1, –y + 1, –z + 1.]

9-(2-Bromophenoxycarbonyl)-10-methylacridinium trifluoromethanesulfonate top

Crystal data top

C₂₁H₁₅BrNO₂⁺·CF₃O₃S⁻	F(000) = 1088
M_r = 542.32	D_x = 1.707 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1539 reflections
a = 12.5718 (8) Å	θ = 3.0–29.2°
b = 20.3617 (16) Å	µ = 2.11 mm⁻¹
c = 8.5162 (6) Å	T = 295 K
β = 104.498 (7)°	Plate, light-orange
V = 2110.6 (3) Å³	0.46 × 0.25 × 0.02 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3735 independent reflections
Radiation source: Enhanced (Mo) X-ray Source	2348 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 10.4002 pixels mm^-1	θ_max = 25.1°, θ_min = 3.2°
ω scans	h = −14→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −24→23
T_min = 0.668, T_max = 1.000	l = −10→10
16372 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 0.92	w = 1/[σ²(F_o²) + (0.0518P)²] where P = (F_o² + 2F_c²)/3
3735 reflections	(Δ/σ)_max = 0.001
299 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₁H₁₅BrNO₂⁺·CF₃O₃S⁻	V = 2110.6 (3) Å³
M_r = 542.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5718 (8) Å	µ = 2.11 mm⁻¹
b = 20.3617 (16) Å	T = 295 K
c = 8.5162 (6) Å	0.46 × 0.25 × 0.02 mm
β = 104.498 (7)°

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3735 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	2348 reflections with I > 2σ(I)
T_min = 0.668, T_max = 1.000	R_int = 0.041
16372 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 0.92	Δρ_max = 0.46 e Å⁻³
3735 reflections	Δρ_min = −0.40 e Å⁻³
299 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.5650 (3)	0.70124 (15)	0.5969 (4)	0.0507 (8)
H1	0.5048	0.7209	0.6227	0.061*
C2	0.6310 (3)	0.73723 (16)	0.5286 (4)	0.0575 (9)
H2	0.6170	0.7818	0.5098	0.069*
C3	0.7204 (3)	0.70832 (18)	0.4856 (4)	0.0581 (9)
H3	0.7639	0.7337	0.4355	0.070*
C4	0.7451 (3)	0.64367 (16)	0.5157 (3)	0.0517 (8)
H4	0.8048	0.6252	0.4860	0.062*
C5	0.6664 (3)	0.43392 (15)	0.7299 (4)	0.0532 (8)
H5	0.7314	0.4166	0.7140	0.064*
C6	0.5970 (3)	0.39546 (15)	0.7872 (4)	0.0586 (9)
H6	0.6154	0.3516	0.8099	0.070*
C7	0.4988 (3)	0.41906 (15)	0.8135 (4)	0.0525 (8)
H7	0.4519	0.3910	0.8503	0.063*
C8	0.4724 (2)	0.48279 (14)	0.7851 (3)	0.0457 (7)
H8	0.4078	0.4988	0.8052	0.055*
C9	0.5181 (2)	0.59299 (13)	0.6949 (3)	0.0355 (7)
N10	0.70556 (19)	0.54005 (11)	0.6297 (2)	0.0397 (6)
C11	0.5865 (2)	0.63282 (13)	0.6305 (3)	0.0379 (7)
C12	0.6800 (2)	0.60492 (14)	0.5919 (3)	0.0405 (7)
C13	0.5419 (2)	0.52598 (13)	0.7246 (3)	0.0366 (7)
C14	0.6396 (2)	0.50086 (13)	0.6942 (3)	0.0380 (7)
C15	0.4213 (2)	0.62290 (13)	0.7426 (3)	0.0388 (7)
O16	0.32648 (15)	0.60104 (8)	0.6463 (2)	0.0410 (5)
O17	0.42777 (16)	0.66151 (10)	0.8497 (2)	0.0541 (6)
C18	0.2280 (2)	0.62507 (14)	0.6773 (3)	0.0417 (7)
C19	0.1815 (2)	0.68158 (14)	0.6025 (3)	0.0457 (8)
C20	0.0812 (3)	0.70147 (17)	0.6251 (4)	0.0596 (9)
H20	0.0476	0.7392	0.5743	0.072*
C21	0.0311 (3)	0.6654 (2)	0.7228 (4)	0.0664 (10)
H21	−0.0362	0.6791	0.7382	0.080*
C22	0.0792 (3)	0.60940 (19)	0.7976 (4)	0.0637 (10)
H22	0.0449	0.5855	0.8639	0.076*
C23	0.1787 (3)	0.58855 (15)	0.7748 (4)	0.0509 (8)
H23	0.2117	0.5505	0.8245	0.061*
Br24	0.25462 (3)	0.731793 (18)	0.47628 (4)	0.06770 (16)
C25	0.8105 (3)	0.51466 (16)	0.6062 (4)	0.0605 (9)
H25A	0.8261	0.4728	0.6587	0.091*
H25B	0.8685	0.5449	0.6522	0.091*
H25C	0.8050	0.5098	0.4923	0.091*
S26	0.17372 (8)	0.40673 (5)	0.95720 (10)	0.0608 (3)
O27	0.2606 (2)	0.41546 (17)	0.8843 (4)	0.1142 (11)
O28	0.1816 (3)	0.35388 (13)	1.0698 (3)	0.0968 (9)
O29	0.1332 (2)	0.46570 (12)	1.0126 (3)	0.0852 (8)
C30	0.0621 (3)	0.38096 (18)	0.7915 (4)	0.0625 (9)
F31	0.0855 (2)	0.32387 (11)	0.7309 (3)	0.0976 (7)
F32	0.0450 (2)	0.42450 (12)	0.6698 (2)	0.0985 (7)
F33	−0.03080 (19)	0.37394 (13)	0.8308 (3)	0.1006 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.044 (2)	0.0501 (19)	0.0606 (18)	0.0065 (16)	0.0176 (16)	0.0073 (15)
C2	0.056 (2)	0.0465 (18)	0.072 (2)	−0.0008 (17)	0.0180 (19)	0.0134 (16)
C3	0.053 (2)	0.063 (2)	0.061 (2)	−0.0112 (18)	0.0200 (17)	0.0060 (16)
C4	0.045 (2)	0.060 (2)	0.0563 (18)	−0.0036 (17)	0.0233 (16)	−0.0003 (15)
C5	0.053 (2)	0.0488 (19)	0.0603 (19)	0.0127 (17)	0.0193 (16)	−0.0009 (15)
C6	0.068 (3)	0.0403 (18)	0.068 (2)	0.0100 (18)	0.0181 (19)	0.0076 (15)
C7	0.051 (2)	0.050 (2)	0.0576 (19)	−0.0015 (17)	0.0163 (16)	0.0083 (15)
C8	0.0402 (19)	0.0512 (19)	0.0463 (16)	0.0000 (15)	0.0122 (14)	0.0017 (14)
C9	0.0288 (16)	0.0437 (17)	0.0319 (13)	0.0022 (13)	0.0035 (12)	−0.0038 (12)
N10	0.0327 (14)	0.0451 (14)	0.0426 (13)	0.0004 (12)	0.0120 (11)	−0.0088 (11)
C11	0.0318 (17)	0.0444 (17)	0.0365 (14)	−0.0006 (14)	0.0065 (13)	0.0004 (12)
C12	0.0351 (18)	0.0513 (19)	0.0350 (14)	−0.0040 (15)	0.0086 (13)	−0.0073 (13)
C13	0.0297 (17)	0.0463 (18)	0.0328 (14)	0.0000 (13)	0.0058 (12)	−0.0044 (12)
C14	0.0345 (18)	0.0438 (18)	0.0342 (14)	0.0004 (14)	0.0056 (13)	−0.0061 (12)
C15	0.0392 (19)	0.0388 (16)	0.0392 (16)	0.0002 (14)	0.0112 (14)	0.0036 (13)
O16	0.0297 (11)	0.0477 (11)	0.0461 (11)	0.0011 (9)	0.0102 (9)	−0.0073 (9)
O17	0.0409 (13)	0.0674 (14)	0.0534 (12)	−0.0011 (11)	0.0105 (10)	−0.0193 (11)
C18	0.0297 (17)	0.0493 (18)	0.0453 (15)	0.0000 (15)	0.0079 (13)	−0.0118 (14)
C19	0.0331 (19)	0.0549 (19)	0.0455 (16)	0.0011 (15)	0.0031 (14)	−0.0113 (14)
C20	0.045 (2)	0.065 (2)	0.062 (2)	0.0092 (19)	−0.0010 (17)	−0.0164 (18)
C21	0.032 (2)	0.091 (3)	0.076 (2)	−0.001 (2)	0.0114 (19)	−0.033 (2)
C22	0.048 (2)	0.085 (3)	0.062 (2)	−0.016 (2)	0.0208 (18)	−0.0191 (19)
C23	0.042 (2)	0.0555 (19)	0.0585 (19)	−0.0048 (16)	0.0189 (16)	−0.0061 (15)
Br24	0.0705 (3)	0.0676 (3)	0.0633 (2)	0.01066 (19)	0.01349 (18)	0.01921 (17)
C25	0.045 (2)	0.058 (2)	0.086 (2)	0.0032 (17)	0.0298 (18)	−0.0099 (18)
S26	0.0498 (6)	0.0710 (6)	0.0608 (5)	−0.0004 (4)	0.0121 (4)	−0.0092 (4)
O27	0.0577 (19)	0.157 (3)	0.143 (3)	−0.0291 (19)	0.0528 (18)	−0.044 (2)
O28	0.130 (3)	0.0818 (18)	0.0673 (15)	0.0238 (17)	0.0033 (16)	0.0126 (14)
O29	0.108 (2)	0.0632 (16)	0.0888 (17)	0.0013 (15)	0.0326 (16)	−0.0232 (13)
C30	0.060 (3)	0.074 (3)	0.061 (2)	−0.008 (2)	0.0304 (19)	−0.0021 (19)
F31	0.123 (2)	0.0832 (16)	0.0873 (14)	−0.0155 (14)	0.0280 (14)	−0.0331 (12)
F32	0.1056 (19)	0.1177 (19)	0.0672 (13)	0.0148 (15)	0.0119 (13)	0.0236 (13)
F33	0.0587 (15)	0.140 (2)	0.1082 (17)	−0.0275 (14)	0.0301 (13)	−0.0134 (15)

Geometric parameters (Å, º) top

C1—C2	1.343 (4)	C13—C14	1.412 (4)
C1—C11	1.434 (4)	C15—O17	1.192 (3)
C1—H1	0.9300	C15—O16	1.342 (3)
C2—C3	1.397 (5)	O16—C18	1.417 (3)
C2—H2	0.9300	C18—C23	1.372 (4)
C3—C4	1.362 (5)	C18—C19	1.373 (4)
C3—H3	0.9300	C19—C20	1.383 (4)
C4—C12	1.407 (4)	C19—Br24	1.882 (3)
C4—H4	0.9300	C20—C21	1.375 (5)
C5—C6	1.351 (4)	C20—H20	0.9300
C5—C14	1.419 (4)	C21—C22	1.371 (5)
C5—H5	0.9300	C21—H21	0.9300
C6—C7	1.394 (4)	C22—C23	1.380 (5)
C6—H6	0.9300	C22—H22	0.9300
C7—C8	1.346 (4)	C23—H23	0.9300
C7—H7	0.9300	C25—H25A	0.9600
C8—C13	1.424 (4)	C25—H25B	0.9600
C8—H8	0.9300	C25—H25C	0.9600
C9—C11	1.391 (4)	S26—O27	1.397 (3)
C9—C13	1.406 (4)	S26—O28	1.428 (3)
C9—C15	1.505 (4)	S26—O29	1.430 (2)
N10—C14	1.362 (3)	S26—C30	1.801 (4)
N10—C12	1.378 (3)	C30—F33	1.301 (4)
N10—C25	1.476 (4)	C30—F31	1.334 (4)
C11—C12	1.416 (4)	C30—F32	1.340 (4)

C2—C1—C11	120.7 (3)	C13—C14—C5	118.7 (3)
C2—C1—H1	119.7	O17—C15—O16	124.5 (3)
C11—C1—H1	119.7	O17—C15—C9	124.6 (3)
C1—C2—C3	120.5 (3)	O16—C15—C9	110.8 (2)
C1—C2—H2	119.7	C15—O16—C18	117.1 (2)
C3—C2—H2	119.7	C23—C18—C19	122.0 (3)
C4—C3—C2	121.2 (3)	C23—C18—O16	118.3 (3)
C4—C3—H3	119.4	C19—C18—O16	119.6 (3)
C2—C3—H3	119.4	C18—C19—C20	118.6 (3)
C3—C4—C12	119.8 (3)	C18—C19—Br24	120.5 (2)
C3—C4—H4	120.1	C20—C19—Br24	120.9 (3)
C12—C4—H4	120.1	C21—C20—C19	120.0 (3)
C6—C5—C14	119.6 (3)	C21—C20—H20	120.0
C6—C5—H5	120.2	C19—C20—H20	120.0
C14—C5—H5	120.2	C22—C21—C20	120.7 (3)
C5—C6—C7	122.4 (3)	C22—C21—H21	119.7
C5—C6—H6	118.8	C20—C21—H21	119.7
C7—C6—H6	118.8	C21—C22—C23	120.0 (3)
C8—C7—C6	119.5 (3)	C21—C22—H22	120.0
C8—C7—H7	120.3	C23—C22—H22	120.0
C6—C7—H7	120.3	C18—C23—C22	118.8 (3)
C7—C8—C13	120.9 (3)	C18—C23—H23	120.6
C7—C8—H8	119.5	C22—C23—H23	120.6
C13—C8—H8	119.5	N10—C25—H25A	109.5
C11—C9—C13	120.8 (3)	N10—C25—H25B	109.5
C11—C9—C15	119.5 (2)	H25A—C25—H25B	109.5
C13—C9—C15	119.6 (3)	N10—C25—H25C	109.5
C14—N10—C12	121.7 (2)	H25A—C25—H25C	109.5
C14—N10—C25	120.3 (2)	H25B—C25—H25C	109.5
C12—N10—C25	117.9 (2)	O27—S26—O28	117.6 (2)
C9—C11—C12	119.2 (3)	O27—S26—O29	115.00 (18)
C9—C11—C1	122.7 (3)	O28—S26—O29	112.46 (17)
C12—C11—C1	118.0 (3)	O27—S26—C30	103.37 (18)
N10—C12—C4	121.1 (3)	O28—S26—C30	102.49 (17)
N10—C12—C11	119.3 (3)	O29—S26—C30	103.38 (17)
C4—C12—C11	119.6 (3)	F33—C30—F31	107.6 (3)
C9—C13—C14	118.3 (3)	F33—C30—F32	106.9 (3)
C9—C13—C8	122.8 (3)	F31—C30—F32	106.6 (3)
C14—C13—C8	118.9 (3)	F33—C30—S26	113.8 (2)
N10—C14—C13	120.5 (2)	F31—C30—S26	110.6 (3)
N10—C14—C5	120.9 (3)	F32—C30—S26	110.8 (2)

C11—C1—C2—C3	1.5 (5)	C8—C13—C14—N10	177.1 (2)
C1—C2—C3—C4	−1.9 (5)	C9—C13—C14—C5	177.5 (2)
C2—C3—C4—C12	−0.2 (4)	C8—C13—C14—C5	−2.0 (4)
C14—C5—C6—C7	−0.1 (5)	C6—C5—C14—N10	−177.1 (3)
C5—C6—C7—C8	−1.7 (5)	C6—C5—C14—C13	2.0 (4)
C6—C7—C8—C13	1.6 (4)	C11—C9—C15—O17	−65.8 (3)
C13—C9—C11—C12	1.2 (4)	C13—C9—C15—O17	110.5 (3)
C15—C9—C11—C12	177.5 (2)	C11—C9—C15—O16	113.1 (3)
C13—C9—C11—C1	179.5 (2)	C13—C9—C15—O16	−70.5 (3)
C15—C9—C11—C1	−4.3 (4)	O17—C15—O16—C18	−1.1 (4)
C2—C1—C11—C9	−177.3 (3)	C9—C15—O16—C18	179.9 (2)
C2—C1—C11—C12	1.0 (4)	C15—O16—C18—C23	−94.4 (3)
C14—N10—C12—C4	−175.8 (2)	C15—O16—C18—C19	89.3 (3)
C25—N10—C12—C4	7.3 (4)	C23—C18—C19—C20	−0.9 (4)
C14—N10—C12—C11	4.1 (3)	O16—C18—C19—C20	175.3 (2)
C25—N10—C12—C11	−172.7 (2)	C23—C18—C19—Br24	177.7 (2)
C3—C4—C12—N10	−177.4 (3)	O16—C18—C19—Br24	−6.2 (3)
C3—C4—C12—C11	2.7 (4)	C18—C19—C20—C21	1.0 (4)
C9—C11—C12—N10	−4.6 (3)	Br24—C19—C20—C21	−177.5 (2)
C1—C11—C12—N10	177.0 (2)	C19—C20—C21—C22	−0.4 (5)
C9—C11—C12—C4	175.3 (2)	C20—C21—C22—C23	−0.3 (5)
C1—C11—C12—C4	−3.0 (4)	C19—C18—C23—C22	0.2 (4)
C11—C9—C13—C14	2.7 (3)	O16—C18—C23—C22	−176.0 (2)
C15—C9—C13—C14	−173.5 (2)	C21—C22—C23—C18	0.4 (4)
C11—C9—C13—C8	−177.8 (2)	O27—S26—C30—F33	−175.8 (3)
C15—C9—C13—C8	6.0 (4)	O28—S26—C30—F33	61.5 (3)
C7—C8—C13—C9	−179.3 (2)	O29—S26—C30—F33	−55.6 (3)
C7—C8—C13—C14	0.2 (4)	O27—S26—C30—F31	62.8 (3)
C12—N10—C14—C13	0.0 (3)	O28—S26—C30—F31	−59.9 (3)
C25—N10—C14—C13	176.7 (2)	O29—S26—C30—F31	−177.0 (2)
C12—N10—C14—C5	179.0 (2)	O27—S26—C30—F32	−55.2 (3)
C25—N10—C14—C5	−4.2 (4)	O28—S26—C30—F32	−177.9 (3)
C9—C13—C14—N10	−3.4 (3)	O29—S26—C30—F32	65.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O28ⁱ	0.93	2.54	3.289 (5)	137
C7—H7···O27	0.93	2.54	3.200 (5)	128

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₅BrNO₂⁺·CF₃O₃S⁻
M_r	542.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	12.5718 (8), 20.3617 (16), 8.5162 (6)
β (°)	104.498 (7)
V (Å³)	2110.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.11
Crystal size (mm)	0.46 × 0.25 × 0.02

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.668, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16372, 3735, 2348
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.088, 0.92
No. of reflections	3735
No. of parameters	299
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.40

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O28ⁱ	0.93	2.54	3.289 (5)	137
C7—H7···O27	0.93	2.54	3.200 (5)	128

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

C—F···π, C—Br···π and S—O···π interactions (Å, °). top

Cg1, Cg2 and Cg4 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C18–C23 rings, respectively.

X—I···J	I···J	X···J	X—I···J
C19—Br24···Cg4ⁱⁱ	3.523 (2)	4.847 (3)	124.6 (1)
C30—F32···Cg4ⁱⁱⁱ	3.648 (2)	4.310 (4)	110.8 (2)
S26—O27···Cg1^iv	3.821 (3)	3.708 (2)	74.8 (2)
S26—O28···Cg1^iv	3.414 (3)	3.708 (2)	90.3 (2)
S26—O28···Cg2^iv	3.358 (3)	4.445 (2)	132.2 (2)

Symmetry codes: (ii) x, –y + 3/2, z – 1/2; (iii) –x, –y + 1, –z + 1; (iv) –x + 1, –y + 1, –z + 2.

π–π interactions (Å, °). top

Cg1 and Cg3 are the centroids of the C9/N10/C11–C14 and C5–C8/C13/C14 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.

I	J	CgI···CgJ	Dihedral angle	CgI_Perp	CgI_Offset
1	3^v	3.744 (2)	2.74 (13)	3.703 (2)	0.553 (2)
3	1^v	3.744 (2)	2.74 (13)	3.717 (2)	0.549 (2)

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

Acknowledgements

This study was financed by the State Funds for Scientific Research through National Center for Science grant No. N N204 375 740 (contract No. 3757/B/H03/2011/40). DT acknowledges financial support from the European Social Fund within the project "Educators for the elite - integrated training program for PhD students, post-docs and professors as academic teachers at the University of Gdańsk" and the Human Capital Operational Program Action 4.1.1, Improving the quality on offer at tertiary educational institutions. This publication reflects the views only of the author: the sponsor cannot be held responsible for any use which may be made of the information contained therein.

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