9-(Methyl-sulfan-yl)acridinium trifluoro-methane-sulfonate.

In the crystal structure of the title compound, C(14)H(12)NS(+)·CF(3)SO(3) (-), N-H⋯O hydrogen bonds link cations and anions into ion pairs. Inversely oriented ion pairs form stacks through multidirectional π-π inter-actions among the acridine units. The crystal structure features a network of C-H⋯O inter-actions among stacks and also long-range electrostatic inter-actions among ions. In the packing of the mol-ecules, the acridine units are nearly parallel in stacks or inclined at an angle of 33.07 (2)° in the four adjacent stacks with which they inter-act via weak C-H⋯O inter-actions. The methyl-sulfanyl group is twisted through an angle of 60.53 (2)° with respect to the acridine ring.

Related literature

For general background, see: Wróblewska et al. (2004 ▶); Zomer & Jacquemijns (2001 ▶). For related structures, see: Meszko et al. (2002 ▶); Mrozek et al. (2002 ▶); Storoniak et al. (2000 ▶). For mol­ecular inter­actions, see: Aakeröy et al. (1992 ▶); Bianchi et al. (2004 ▶); Hunter et al. (2001 ▶); Spek (2009 ▶); Steiner (1991 ▶). For the synthesis, see: Berny et al. (1992 ▶); Sato (1996 ▶).

Experimental

Crystal data

C14H12NS+·CF3SO3 −

M = 375.40

Monoclinic,

a = 7.2992 (2) Å

b = 17.3090 (6) Å

c = 13.0582 (4) Å

β = 103.910 (3)°

V = 1601.42 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.38 mm−1

T = 295 K

0.45 × 0.40 × 0.20 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer

Absorption correction: none

13308 measured reflections

2841 independent reflections

1944 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.161

S = 1.06

2841 reflections

226 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.35 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004978/ng2540sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004978/ng2540Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H12NS+·CF3SO3−	F(000) = 768
Mr = 375.40	Dx = 1.557 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5491 reflections
a = 7.2992 (2) Å	θ = 3.1–29.2°
b = 17.3090 (6) Å	µ = 0.38 mm−1
c = 13.0582 (4) Å	T = 295 K
β = 103.910 (3)°	Block, yellow
V = 1601.42 (9) Å3	0.45 × 0.4 × 0.2 mm
Z = 4

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	1944 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	Rint = 0.028
graphite	θmax = 25.1°, θmin = 3.1°
Detector resolution: 10.4002 pixels mm-1	h = −8→8
ω scans	k = −20→20
13308 measured reflections	l = −15→15
2841 independent reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.1054P)2] where P = (Fo2 + 2Fc2)/3
2841 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.51 e Å−3
1 restraint	Δρmin = −0.35 e Å−3

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	−0.0169 (4)	1.03470 (19)	0.2103 (2)	0.0567 (7)
H1	−0.0740	1.0824	0.1916	0.068*
C2	−0.0343 (4)	0.9785 (2)	0.1374 (2)	0.0702 (9)
H2	−0.1039	0.9879	0.0690	0.084*
C3	0.0508 (5)	0.9058 (2)	0.1626 (3)	0.0751 (10)
H3	0.0404	0.8684	0.1103	0.090*
C4	0.1478 (4)	0.8897 (2)	0.2624 (3)	0.0630 (8)
H4	0.2023	0.8414	0.2791	0.076*
C5	0.3767 (3)	0.9596 (2)	0.6240 (2)	0.0577 (8)
H5	0.4190	0.9092	0.6380	0.069*
C6	0.4067 (4)	1.0138 (2)	0.7023 (2)	0.0657 (9)
H6	0.4717	0.9998	0.7700	0.079*
C7	0.3425 (4)	1.0895 (2)	0.6832 (3)	0.0670 (9)
H7	0.380 (4)	1.127 (2)	0.742 (3)	0.079 (10)*
C8	0.2485 (4)	1.11202 (18)	0.5862 (2)	0.0573 (7)
H8	0.2070	1.1628	0.5750	0.069*
C9	0.1176 (3)	1.07880 (15)	0.3956 (2)	0.0442 (6)
N10	0.2546 (3)	0.93052 (14)	0.44086 (19)	0.0478 (6)
H10	0.300 (4)	0.8858 (12)	0.462 (2)	0.071 (10)*
C11	0.0877 (3)	1.02193 (16)	0.3156 (2)	0.0453 (6)
C12	0.1652 (3)	0.94706 (16)	0.3405 (2)	0.0455 (6)
C13	0.2116 (3)	1.05863 (16)	0.49974 (19)	0.0438 (6)
C14	0.2796 (3)	0.98202 (16)	0.5208 (2)	0.0441 (6)
S15	0.03215 (12)	1.17329 (5)	0.36941 (8)	0.0731 (3)
C16	0.1546 (5)	1.2067 (2)	0.2729 (3)	0.0770 (10)
H16A	0.1099	1.2572	0.2488	0.116*
H16B	0.1314	1.1716	0.2142	0.116*
H16C	0.2877	1.2089	0.3044	0.116*
S17	0.36383 (10)	0.71528 (5)	0.50824 (6)	0.0577 (3)
O18	0.4183 (4)	0.6911 (2)	0.6130 (2)	0.1215 (12)
O19	0.4246 (4)	0.79237 (14)	0.4965 (3)	0.1040 (10)
O20	0.1780 (3)	0.6955 (2)	0.4545 (2)	0.1045 (10)
C21	0.5109 (6)	0.6611 (3)	0.4413 (4)	0.0960 (13)
F22	0.4700 (5)	0.6751 (3)	0.3414 (3)	0.193 (2)
F23	0.4819 (6)	0.5867 (2)	0.4487 (4)	0.2000 (19)
F24	0.6911 (3)	0.67460 (17)	0.4790 (3)	0.1366 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0519 (15)	0.068 (2)	0.0489 (15)	0.0013 (14)	0.0100 (12)	0.0050 (15)
C2	0.0620 (18)	0.096 (3)	0.0504 (17)	−0.0082 (18)	0.0092 (14)	−0.0036 (18)
C3	0.0695 (19)	0.092 (3)	0.067 (2)	−0.0095 (19)	0.0227 (17)	−0.031 (2)
C4	0.0542 (16)	0.059 (2)	0.077 (2)	0.0015 (14)	0.0176 (15)	−0.0158 (16)
C5	0.0438 (14)	0.070 (2)	0.0586 (18)	−0.0061 (13)	0.0101 (13)	0.0162 (16)
C6	0.0537 (16)	0.095 (3)	0.0466 (17)	−0.0186 (17)	0.0077 (13)	0.0052 (17)
C7	0.0646 (18)	0.086 (3)	0.0510 (18)	−0.0206 (18)	0.0156 (15)	−0.0155 (18)
C8	0.0582 (16)	0.0533 (19)	0.0639 (19)	−0.0093 (13)	0.0218 (14)	−0.0097 (14)
C9	0.0383 (12)	0.0407 (16)	0.0555 (16)	0.0005 (11)	0.0151 (11)	0.0019 (12)
N10	0.0417 (11)	0.0395 (14)	0.0618 (15)	0.0004 (10)	0.0118 (10)	0.0048 (12)
C11	0.0379 (12)	0.0494 (17)	0.0499 (15)	0.0018 (11)	0.0129 (11)	0.0016 (12)
C12	0.0375 (12)	0.0475 (17)	0.0534 (16)	−0.0055 (11)	0.0144 (11)	−0.0059 (13)
C13	0.0400 (12)	0.0448 (16)	0.0496 (15)	−0.0082 (11)	0.0166 (11)	−0.0039 (12)
C14	0.0353 (12)	0.0488 (17)	0.0489 (15)	−0.0069 (11)	0.0113 (11)	0.0023 (12)
S15	0.0800 (6)	0.0507 (6)	0.0909 (7)	0.0178 (4)	0.0248 (5)	0.0059 (4)
C16	0.083 (2)	0.056 (2)	0.087 (2)	−0.0126 (17)	0.0096 (19)	0.0185 (17)
S17	0.0620 (5)	0.0550 (5)	0.0527 (5)	−0.0016 (3)	0.0070 (3)	0.0084 (3)
O18	0.124 (2)	0.173 (3)	0.0551 (15)	−0.023 (2)	−0.0018 (15)	0.0306 (16)
O19	0.1003 (18)	0.0507 (16)	0.172 (3)	0.0158 (13)	0.0536 (18)	0.0300 (16)
O20	0.0605 (14)	0.159 (3)	0.0864 (18)	−0.0124 (15)	0.0026 (13)	−0.0175 (17)
C21	0.077 (3)	0.081 (3)	0.122 (4)	0.005 (2)	0.007 (2)	−0.023 (3)
F22	0.144 (3)	0.345 (6)	0.097 (2)	0.028 (3)	0.044 (2)	−0.063 (3)
F23	0.177 (3)	0.085 (2)	0.331 (6)	−0.001 (2)	0.047 (3)	−0.088 (3)
F24	0.0666 (14)	0.132 (2)	0.199 (3)	0.0187 (13)	0.0096 (15)	−0.057 (2)

C1—C2	1.346 (4)	C9—C11	1.414 (4)
C1—C11	1.421 (4)	C9—S15	1.754 (3)
C1—H1	0.9300	N10—C12	1.347 (3)
C2—C3	1.407 (5)	N10—C14	1.351 (3)
C2—H2	0.9300	N10—H10	0.860 (18)
C3—C4	1.354 (4)	C11—C12	1.420 (4)
C3—H3	0.9300	C13—C14	1.419 (4)
C4—C12	1.407 (4)	S15—C16	1.807 (4)
C4—H4	0.9300	C16—H16A	0.9600
C5—C6	1.365 (5)	C16—H16B	0.9600
C5—C14	1.417 (4)	C16—H16C	0.9600
C5—H5	0.9300	S17—O18	1.393 (3)
C6—C7	1.394 (5)	S17—O20	1.411 (2)
C6—H6	0.9300	S17—O19	1.426 (3)
C7—C8	1.346 (4)	S17—C21	1.803 (5)
C7—H7	1.00 (4)	C21—F22	1.289 (6)
C8—C13	1.433 (4)	C21—F23	1.312 (5)
C8—H8	0.9300	C21—F24	1.310 (5)
C9—C13	1.412 (4)
C2—C1—C11	120.6 (3)	C9—C11—C1	124.0 (3)
C2—C1—H1	119.7	C12—C11—C1	117.1 (2)
C11—C1—H1	119.7	N10—C12—C4	119.6 (3)
C1—C2—C3	121.4 (3)	N10—C12—C11	119.4 (2)
C1—C2—H2	119.3	C4—C12—C11	121.1 (3)
C3—C2—H2	119.3	C9—C13—C14	119.0 (2)
C4—C3—C2	120.5 (3)	C9—C13—C8	123.7 (3)
C4—C3—H3	119.7	C14—C13—C8	117.3 (2)
C2—C3—H3	119.7	N10—C14—C13	119.4 (2)
C3—C4—C12	119.2 (3)	N10—C14—C5	119.9 (3)
C3—C4—H4	120.4	C13—C14—C5	120.8 (3)
C12—C4—H4	120.4	C9—S15—C16	102.83 (15)
C6—C5—C14	118.5 (3)	S15—C16—H16A	109.5
C6—C5—H5	120.7	S15—C16—H16B	109.5
C14—C5—H5	120.7	H16A—C16—H16B	109.5
C5—C6—C7	121.7 (3)	S15—C16—H16C	109.5
C5—C6—H6	119.2	H16A—C16—H16C	109.5
C7—C6—H6	119.2	H16B—C16—H16C	109.5
C8—C7—C6	120.9 (3)	O18—S17—O20	115.38 (19)
C8—C7—H7	121 (2)	O18—S17—O19	111.4 (2)
C6—C7—H7	117 (2)	O20—S17—O19	117.40 (19)
C7—C8—C13	120.8 (3)	O18—S17—C21	104.9 (2)
C7—C8—H8	119.6	O20—S17—C21	104.20 (19)
C13—C8—H8	119.6	O19—S17—C21	101.4 (2)
C13—C9—C11	119.5 (2)	F22—C21—F23	105.0 (5)
C13—C9—S15	119.1 (2)	F22—C21—F24	108.3 (4)
C11—C9—S15	121.4 (2)	F23—C21—F24	108.2 (4)
C12—N10—C14	123.7 (2)	F22—C21—S17	111.9 (3)
C12—N10—H10	124 (2)	F23—C21—S17	110.5 (4)
C14—N10—H10	112 (2)	F24—C21—S17	112.7 (3)
C9—C11—C12	118.9 (2)
C11—C1—C2—C3	−0.4 (5)	S15—C9—C13—C8	−2.4 (3)
C1—C2—C3—C4	2.2 (5)	C7—C8—C13—C9	−178.6 (2)
C2—C3—C4—C12	−1.0 (5)	C7—C8—C13—C14	−0.6 (4)
C14—C5—C6—C7	0.8 (4)	C12—N10—C14—C13	−1.0 (4)
C5—C6—C7—C8	−0.2 (5)	C12—N10—C14—C5	−179.6 (2)
C6—C7—C8—C13	0.1 (4)	C9—C13—C14—N10	0.7 (3)
C13—C9—C11—C12	−4.4 (3)	C8—C13—C14—N10	−177.4 (2)
S15—C9—C11—C12	178.03 (18)	C9—C13—C14—C5	179.3 (2)
C13—C9—C11—C1	175.3 (2)	C8—C13—C14—C5	1.2 (3)
S15—C9—C11—C1	−2.3 (3)	C6—C5—C14—N10	177.3 (2)
C2—C1—C11—C9	177.8 (3)	C6—C5—C14—C13	−1.3 (4)
C2—C1—C11—C12	−2.5 (4)	C13—C9—S15—C16	120.7 (2)
C14—N10—C12—C4	179.4 (2)	C11—C9—S15—C16	−61.7 (2)
C14—N10—C12—C11	−1.4 (4)	O18—S17—C21—F22	177.1 (4)
C3—C4—C12—N10	177.3 (3)	O20—S17—C21—F22	55.5 (4)
C3—C4—C12—C11	−1.9 (4)	O19—S17—C21—F22	−66.9 (4)
C9—C11—C12—N10	4.2 (4)	O18—S17—C21—F23	60.6 (4)
C1—C11—C12—N10	−175.6 (2)	O20—S17—C21—F23	−61.0 (4)
C9—C11—C12—C4	−176.7 (2)	O19—S17—C21—F23	176.6 (4)
C1—C11—C12—C4	3.6 (4)	O18—S17—C21—F24	−60.6 (4)
C11—C9—C13—C14	2.0 (3)	O20—S17—C21—F24	177.8 (4)
S15—C9—C13—C14	179.63 (17)	O19—S17—C21—F24	55.4 (4)
C11—C9—C13—C8	−180.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O18i	0.99 (4)	2.38 (4)	3.315 (5)	158 (3)
N10—H10···O19	0.86 (2)	1.86 (2)	2.712 (4)	172 (3)

CgI	CgJ	Cg···Cg	Dihedral angle	Interplanar distance	Offset
Cg1	Cg1ii	3.827 (2)	0.0	3.468 (2)	1.618 (2)
Cg1	Cg3ii	3.634 (2)	1.44	3.474 (2)	1.066 (2)
Cg1	Cg3iii	3.810 (2)	1.44	3.412 (2)	1.695 (2)
Cg2	Cg3ii	3.830 (2)	3.96	3.492 (2)	1.573 (2)
Cg3	Cg1ii	3.634 (2)	1.44	3.483 (2)	1.037 (2)
Cg3	Cg1iii	3.810 (2)	1.44	3.386 (2)	1.747 (2)
Cg3	Cg2ii	3.830 (2)	3.96	3.449 (2)	1.665 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O18i	0.99 (4)	2.38 (4)	3.315 (5)	158 (3)
N10—H10⋯O19	0.86 (2)	1.86 (2)	2.712 (4)	172 (3)

Symmetry code: (i) .

Table 2

π–π Interactions (Å,°)

Cgi	Cgj	Cg⋯Cg	Dihedral angle	Interplanar distance	Offset
Cg1	Cg1ii	3.827 (2)	0.0	3.468 (2)	1.618 (2)
Cg1	Cg3ii	3.634 (2)	1.4	3.474 (2)	1.066 (2)
Cg1	Cg3iii	3.810 (2)	1.4	3.412 (2)	1.695 (2)
Cg2	Cg3ii	3.830 (2)	4.0	3.492 (2)	1.573 (2)
Cg3	Cg1ii	3.634 (2)	1.4	3.483 (2)	1.037 (2)
Cg3	Cg1iii	3.810 (2)	1.4	3.386 (2)	1.747 (2)
Cg3	Cg2ii	3.830 (2)	4.0	3.449 (2)	1.665 (2)

Symmetry codes: (ii) ; (iii) . Notes: Cg1, Cg2 and Cg3 are the centroids of the C9/N10/C11–C14, C1–C4/C11/C12 and C5–C8/C13/C14 rings, respectively. Cg⋯Cg is the distance between ring centroids. The dihedral angle is that between the planes of rings Cg and Cg. The interplanar distance is the perpendicular distance of Cg from ring j. The offset is the perpendicular distance of ring i from ring j.