3,6-Dimethyl-4,5-dihydro-3a,5a-diaza­pyrene ditriflate

Coe, B.J.; Fitzgerald, E.C.; Raftery, J.

doi:10.1107/S1600536806034945

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 10| October 2006| Pages o4333-o4334

https://doi.org/10.1107/S1600536806034945

3,6-Dimethyl-4,5-dihydro-3a,5a-diazapyrene ditriflate

Benjamin J. Coe,^a ^* Emma C. Fitzgerald ^a and James Raftery ^a

^aSchool of Chemistry, University of Manchester, Manchester M13 9PL, England
^*Correspondence e-mail: b.coe@manchester.ac.uk

(Received 23 August 2006; accepted 30 August 2006; online 8 September 2006)

The crystal structure of the title compound, C₁₆H₁₆N₂²⁺·2CF₃O₃S⁻, is the first structure to be reported for a diquaternized derivative of 2,9-dimethyl-1,10-phenanthroline.

Comment

The compound 6,7-dihydrodipyrido[1,2-a:2′,1′-c]pyrazinediium dibromide (diquat dibromide) is a potent herbicide (Brian et al., 1958 ), and related salts derived from 2,2′-bipyridyl and other α-diimines have also generated considerable interest (Summers, 1981 ). In recent years, the attractive redox properties of diquats have led to other uses as electron acceptors in light-harvesting chromophore-quencher systems (Ryu et al., 1992 ; Klumpp et al., 1999 ; Kim et al., 2003 , 2005 ) and in ion-pair charge-transfer complexes (Nunn et al., 1994 ; Hofbauer et al., 1996 ; Unamuno et al., 1998 ; Vitoria et al., 2002 ). Our studies directed at using diquats in novel metal-based chromophore-quencher arrays have afforded an unusually facile method for the synthesis of such compounds, including salts (I) and (II) (Coe, Curati & Fitzgerald, 2006 ). The structure of salt (II), 1,2,7,8-tetramethyl-4,5-dihydro-3a,5a-diazapyrene ditriflate, is presented in the following paper (Coe, Fitzgerald & Raftery, 2006 ).

The molecular structures of the salts (I) (Fig. 1) and (II) are as indicated by ¹H NMR spectroscopy and, to our knowledge, the first to be reported containing these particular methyl-substituted cations. The geometrical parameters of the diquat units are as expected (Table 1), and largely identical for the two compounds. The C atoms of the ethylene bridge have normal tetrahedral geometries, with N1—C13—C14—N2 torsion angles of −58.2 (3)° for (I) and −58.83 (19)° for (II). Comparisons with previously published structures for other diquat compounds derived from 1,10-phenanthroline reveal generally similar bond lengths and angles, although the ethylene torsion angles are somewhat smaller at ca 53–55° (Hofbauer et al., 1996; Unamuno et al., 1998; Vitoria et al., 2002). In both compounds, the presence of the ethylene bridge imparts a small twist to the 3a,5a-diazapyrene unit, with dihedral angles between the two aromatic outer rings of 8.85 (7)° for (I) and 11.26 (5)° for (II). The crystal packing structures of both (I) and (II) reveal extensive C—H⋯O interactions between the diquat cations and the trifluoromethanesulfonate counter-anions.

Figure 1
The asymmetric unit of salt (I)

, showing 50% probability displacement ellipsoids.

Experimental

Salts (I) and (II) were synthesized as reported previously (Coe, Curati & Fitzgerald, 2006). Crystals suitable for single-crystal X-ray diffraction measurements were obtained by slow diffusion of diethyl ether vapour into acetone solutions at 295 K.

Crystal data

C₁₆H₁₆N₂²⁺·2CF₃O₃S⁻
M_r = 534.45
Monoclinic, P 2₁ /c
a = 9.976 (1) Å
b = 12.653 (1) Å
c = 16.559 (2) Å
β = 97.426 (2)°
V = 2072.7 (3) Å³
Z = 4
D_x = 1.713 Mg m⁻³
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 (2) K
Block, white
0.10 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
φ and ω scans
Absorption correction: none
17755 measured reflections
4947 independent reflections
2354 reflections with I > 2σ(I)
R_int = 0.083
θ_max = 28.3°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.064
S = 0.72
4947 reflections
309 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0121P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—N1	1.379 (3)
C1—C9	1.397 (3)
C1—C2	1.427 (3)
C3—N2	1.344 (3)
C3—C4	1.397 (3)
C3—C15	1.486 (3)
C4—C5	1.360 (3)
C5—C6	1.402 (3)
C6—C7	1.416 (3)
C7—C8	1.348 (3)
C10—C11	1.352 (3)
C11—C12	1.403 (3)
C13—N1	1.481 (3)
C13—C14	1.498 (3)

N1—C1—C2	121.3 (2)
N2—C2—C1	120.8 (2)
N1—C13—C14	109.9 (2)
N2—C14—C13	110.2 (2)
C1—N1—C13	116.6 (2)
C2—N2—C14	115.4 (2)

N1—C13—C14—N2	−58.2 (3)

All H atoms were included in calculated positions, with C—H = 0.95 (CH), 0.99 (CH₂) and 0.98 Å (CH₃). U_iso(H) values were fixed at 1.2U_eq(C) or 1.5U_eq(methyl C).

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806034945/ga2004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806034945/ga2004Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

3,6-Dimethyl-4,5-dihydro-3a,5a-diazapyrene ditriflate top

Crystal data top

C₁₆H₁₆N₂²⁺·2CF₃O₃S⁻	F(000) = 1088
M_r = 534.45	D_x = 1.713 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.9760 (9) Å	Cell parameters from 1610 reflections
b = 12.6530 (12) Å	θ = 2.5–21.7°
c = 16.5590 (15) Å	µ = 0.35 mm⁻¹
β = 97.426 (2)°	T = 100 K
V = 2072.7 (3) Å³	Block, white
Z = 4	0.10 × 0.10 × 0.05 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2354 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.083
Graphite monochromator	θ_max = 28.3°, θ_min = 2.0°
φ and ω scans	h = −13→13
17755 measured reflections	k = −16→16
4947 independent reflections	l = −21→21

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 0.72	w = 1/[σ²(F_o²) + (0.0121P)²] where P = (F_o² + 2F_c²)/3
4947 reflections	(Δ/σ)_max < 0.001
309 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1567 (3)	0.1077 (2)	0.15172 (14)	0.0174 (6)
C2	0.0181 (3)	0.1359 (2)	0.13050 (15)	0.0167 (6)
C3	−0.1544 (3)	0.2676 (2)	0.12110 (15)	0.0190 (6)
C4	−0.2452 (3)	0.1945 (2)	0.08142 (15)	0.0230 (7)
H4	−0.3342	0.2164	0.0609	0.028*
C5	−0.2075 (3)	0.0925 (2)	0.07179 (14)	0.0222 (7)
H5	−0.2721	0.0428	0.0478	0.027*
C6	−0.0743 (3)	0.0598 (2)	0.09695 (15)	0.0188 (7)
C7	−0.0315 (3)	−0.0463 (2)	0.09105 (15)	0.0248 (7)
H7	−0.0949	−0.0983	0.0695	0.030*
C8	0.0976 (3)	−0.0747 (2)	0.11544 (15)	0.0251 (7)
H8	0.1233	−0.1468	0.1131	0.030*
C9	0.1952 (3)	0.0023 (2)	0.14464 (15)	0.0193 (6)
C10	0.3325 (3)	−0.0229 (2)	0.16485 (15)	0.0252 (7)
H10	0.3610	−0.0942	0.1614	0.030*
C11	0.4247 (3)	0.0527 (2)	0.18913 (15)	0.0248 (7)
H11	0.5170	0.0340	0.2033	0.030*
C12	0.3847 (3)	0.1586 (2)	0.19352 (15)	0.0203 (7)
C13	0.2087 (2)	0.29466 (19)	0.17123 (15)	0.0188 (6)
H13A	0.2072	0.3208	0.1148	0.023*
H13B	0.2730	0.3387	0.2073	0.023*
C14	0.0704 (2)	0.30377 (19)	0.19652 (15)	0.0180 (6)
H14A	0.0731	0.2815	0.2540	0.022*
H14B	0.0402	0.3783	0.1922	0.022*
C15	−0.1984 (2)	0.37606 (18)	0.13973 (15)	0.0228 (7)
H15A	−0.1960	0.3841	0.1988	0.034*
H15B	−0.2907	0.3879	0.1131	0.034*
H15C	−0.1375	0.4278	0.1196	0.034*
C16	0.4851 (2)	0.2445 (2)	0.21452 (15)	0.0268 (7)
H16A	0.4811	0.2946	0.1691	0.040*
H16B	0.5760	0.2140	0.2248	0.040*
H16C	0.4644	0.2814	0.2634	0.040*
C17	0.8492 (3)	0.0991 (2)	0.41836 (16)	0.0226 (7)
C18	0.3750 (3)	0.1503 (2)	0.44510 (19)	0.0326 (8)
F1	0.87856 (15)	0.00203 (12)	0.44659 (9)	0.0344 (4)
F2	0.94339 (16)	0.16427 (11)	0.45590 (9)	0.0313 (4)
F3	0.73160 (15)	0.12689 (13)	0.44114 (9)	0.0394 (5)
F4	0.43119 (17)	0.10610 (13)	0.38467 (9)	0.0454 (5)
F5	0.25290 (18)	0.11155 (14)	0.44460 (11)	0.0623 (6)
F6	0.44811 (18)	0.11972 (12)	0.51482 (10)	0.0517 (6)
N1	0.2535 (2)	0.18299 (16)	0.17606 (12)	0.0176 (5)
N2	−0.0262 (2)	0.23661 (16)	0.14401 (12)	0.0164 (5)
O1	0.97977 (17)	0.06831 (13)	0.29701 (10)	0.0249 (5)
O2	0.73879 (17)	0.02953 (13)	0.28035 (10)	0.0259 (5)
O3	0.81677 (17)	0.21236 (13)	0.28858 (10)	0.0224 (5)
O4	0.51139 (18)	0.32162 (14)	0.44150 (12)	0.0380 (6)
O5	0.30593 (19)	0.32464 (14)	0.50635 (10)	0.0333 (5)
O6	0.29322 (18)	0.31170 (15)	0.35924 (10)	0.0367 (6)
S1	0.84551 (7)	0.10272 (5)	0.30835 (4)	0.01910 (17)
S2	0.37134 (7)	0.29347 (6)	0.43738 (4)	0.02275 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0226 (16)	0.0185 (15)	0.0118 (14)	−0.0006 (14)	0.0055 (12)	0.0023 (12)
C2	0.0208 (16)	0.0182 (16)	0.0119 (14)	0.0005 (13)	0.0052 (12)	0.0022 (12)
C3	0.0205 (16)	0.0247 (17)	0.0127 (15)	−0.0008 (13)	0.0059 (13)	0.0033 (12)
C4	0.0207 (17)	0.0312 (18)	0.0168 (15)	−0.0008 (14)	0.0017 (13)	0.0008 (14)
C5	0.0228 (18)	0.0275 (18)	0.0167 (15)	−0.0107 (14)	0.0042 (13)	−0.0017 (13)
C6	0.0247 (17)	0.0205 (16)	0.0124 (15)	−0.0051 (13)	0.0067 (13)	0.0003 (12)
C7	0.043 (2)	0.0167 (17)	0.0164 (16)	−0.0101 (14)	0.0088 (15)	−0.0025 (12)
C8	0.045 (2)	0.0155 (16)	0.0171 (16)	0.0054 (15)	0.0112 (14)	0.0024 (13)
C9	0.0302 (18)	0.0161 (16)	0.0125 (15)	0.0027 (14)	0.0067 (13)	0.0028 (12)
C10	0.039 (2)	0.0168 (16)	0.0214 (17)	0.0129 (15)	0.0075 (15)	0.0052 (13)
C11	0.0231 (18)	0.0328 (19)	0.0186 (17)	0.0127 (15)	0.0030 (14)	0.0035 (14)
C12	0.0181 (16)	0.0319 (18)	0.0115 (15)	0.0032 (14)	0.0046 (12)	0.0010 (12)
C13	0.0182 (16)	0.0151 (15)	0.0225 (16)	−0.0010 (13)	0.0002 (12)	0.0030 (13)
C14	0.0202 (16)	0.0156 (15)	0.0175 (15)	−0.0001 (13)	−0.0003 (12)	0.0001 (12)
C15	0.0207 (16)	0.0218 (17)	0.0263 (17)	0.0032 (13)	0.0042 (13)	0.0027 (13)
C16	0.0164 (17)	0.0395 (19)	0.0247 (17)	0.0012 (14)	0.0035 (13)	0.0040 (14)
C17	0.0247 (17)	0.0223 (17)	0.0209 (16)	0.0038 (15)	0.0038 (14)	0.0012 (14)
C18	0.040 (2)	0.0323 (19)	0.0269 (19)	−0.0026 (17)	0.0094 (17)	−0.0039 (16)
F1	0.0492 (11)	0.0270 (10)	0.0253 (10)	−0.0003 (9)	−0.0012 (8)	0.0095 (8)
F2	0.0393 (10)	0.0283 (10)	0.0241 (9)	−0.0024 (8)	−0.0042 (8)	−0.0051 (8)
F3	0.0307 (10)	0.0633 (14)	0.0262 (10)	0.0108 (9)	0.0114 (8)	−0.0019 (9)
F4	0.0667 (13)	0.0380 (11)	0.0339 (11)	0.0090 (10)	0.0154 (10)	−0.0086 (9)
F5	0.0548 (13)	0.0509 (13)	0.0855 (16)	−0.0332 (11)	0.0257 (12)	−0.0145 (11)
F6	0.0901 (16)	0.0326 (12)	0.0324 (11)	0.0127 (10)	0.0079 (11)	0.0117 (9)
N1	0.0201 (14)	0.0191 (14)	0.0142 (12)	0.0022 (11)	0.0047 (10)	0.0016 (10)
N2	0.0155 (13)	0.0183 (13)	0.0155 (12)	−0.0021 (10)	0.0031 (10)	0.0013 (10)
O1	0.0234 (11)	0.0304 (12)	0.0226 (11)	0.0059 (9)	0.0089 (9)	0.0030 (9)
O2	0.0290 (12)	0.0187 (11)	0.0279 (12)	−0.0062 (9)	−0.0039 (10)	−0.0006 (9)
O3	0.0327 (12)	0.0128 (10)	0.0211 (11)	0.0003 (9)	0.0012 (9)	0.0017 (8)
O4	0.0237 (12)	0.0378 (14)	0.0516 (15)	−0.0110 (10)	0.0019 (11)	0.0070 (11)
O5	0.0487 (14)	0.0353 (13)	0.0175 (11)	0.0102 (11)	0.0099 (10)	−0.0025 (9)
O6	0.0357 (13)	0.0559 (15)	0.0176 (11)	0.0171 (11)	−0.0006 (10)	0.0024 (10)
S1	0.0236 (4)	0.0181 (4)	0.0154 (4)	0.0003 (4)	0.0019 (3)	0.0009 (3)
S2	0.0232 (4)	0.0237 (4)	0.0209 (4)	0.0011 (4)	0.0012 (3)	0.0021 (3)

Geometric parameters (Å, º) top

C1—N1	1.379 (3)	C13—H13A	0.9900
C1—C9	1.397 (3)	C13—H13B	0.9900
C1—C2	1.427 (3)	C14—N2	1.480 (3)
C2—N2	1.377 (3)	C14—H14A	0.9900
C2—C6	1.398 (3)	C14—H14B	0.9900
C3—N2	1.344 (3)	C15—H15A	0.9800
C3—C4	1.397 (3)	C15—H15B	0.9800
C3—C15	1.486 (3)	C15—H15C	0.9800
C4—C5	1.360 (3)	C16—H16A	0.9800
C4—H4	0.9500	C16—H16B	0.9800
C5—C6	1.402 (3)	C16—H16C	0.9800
C5—H5	0.9500	C17—F3	1.325 (3)
C6—C7	1.416 (3)	C17—F1	1.333 (3)
C7—C8	1.348 (3)	C17—F2	1.342 (3)
C7—H7	0.9500	C17—S1	1.818 (3)
C8—C9	1.419 (3)	C18—F5	1.312 (3)
C8—H8	0.9500	C18—F4	1.332 (3)
C9—C10	1.403 (3)	C18—F6	1.341 (3)
C10—C11	1.352 (3)	C18—S2	1.816 (3)
C10—H10	0.9500	O1—S1	1.4435 (17)
C11—C12	1.403 (3)	O2—S1	1.4418 (17)
C11—H11	0.9500	O3—S1	1.4456 (17)
C12—N1	1.340 (3)	O4—S2	1.4349 (18)
C12—C16	1.488 (3)	O5—S2	1.4417 (18)
C13—N1	1.481 (3)	O6—S2	1.4402 (17)
C13—C14	1.498 (3)

N1—C1—C9	119.6 (2)	N2—C14—H14B	109.6
N1—C1—C2	121.3 (2)	C13—C14—H14B	109.6
C9—C1—C2	119.1 (2)	H14A—C14—H14B	108.1
N2—C2—C6	119.5 (2)	C3—C15—H15A	109.5
N2—C2—C1	120.8 (2)	C3—C15—H15B	109.5
C6—C2—C1	119.6 (2)	H15A—C15—H15B	109.5
N2—C3—C4	118.4 (2)	C3—C15—H15C	109.5
N2—C3—C15	120.4 (2)	H15A—C15—H15C	109.5
C4—C3—C15	121.2 (2)	H15B—C15—H15C	109.5
C5—C4—C3	120.7 (3)	C12—C16—H16A	109.5
C5—C4—H4	119.6	C12—C16—H16B	109.5
C3—C4—H4	119.6	H16A—C16—H16B	109.5
C4—C5—C6	120.7 (3)	C12—C16—H16C	109.5
C4—C5—H5	119.7	H16A—C16—H16C	109.5
C6—C5—H5	119.7	H16B—C16—H16C	109.5
C2—C6—C5	117.8 (2)	F3—C17—F1	107.9 (2)
C2—C6—C7	119.4 (2)	F3—C17—F2	107.3 (2)
C5—C6—C7	122.8 (3)	F1—C17—F2	107.2 (2)
C8—C7—C6	121.2 (3)	F3—C17—S1	111.99 (18)
C8—C7—H7	119.4	F1—C17—S1	110.49 (18)
C6—C7—H7	119.4	F2—C17—S1	111.77 (19)
C7—C8—C9	120.4 (3)	F5—C18—F4	108.6 (2)
C7—C8—H8	119.8	F5—C18—F6	107.4 (3)
C9—C8—H8	119.8	F4—C18—F6	106.9 (2)
C1—C9—C10	117.9 (2)	F5—C18—S2	111.2 (2)
C1—C9—C8	120.0 (3)	F4—C18—S2	111.9 (2)
C10—C9—C8	122.1 (3)	F6—C18—S2	110.6 (2)
C11—C10—C9	121.0 (3)	C12—N1—C1	122.2 (2)
C11—C10—H10	119.5	C12—N1—C13	120.7 (2)
C9—C10—H10	119.5	C1—N1—C13	116.6 (2)
C10—C11—C12	120.3 (3)	C3—N2—C2	122.5 (2)
C10—C11—H11	119.9	C3—N2—C14	121.5 (2)
C12—C11—H11	119.9	C2—N2—C14	115.4 (2)
N1—C12—C11	119.0 (3)	O2—S1—O1	115.05 (11)
N1—C12—C16	119.5 (2)	O2—S1—O3	115.28 (11)
C11—C12—C16	121.5 (2)	O1—S1—O3	114.85 (11)
N1—C13—C14	109.9 (2)	O2—S1—C17	102.96 (12)
N1—C13—H13A	109.7	O1—S1—C17	102.93 (11)
C14—C13—H13A	109.7	O3—S1—C17	103.25 (12)
N1—C13—H13B	109.7	O4—S2—O6	114.42 (12)
C14—C13—H13B	109.7	O4—S2—O5	115.60 (12)
H13A—C13—H13B	108.2	O6—S2—O5	114.84 (11)
N2—C14—C13	110.2 (2)	O4—S2—C18	103.52 (13)
N2—C14—H14A	109.6	O6—S2—C18	103.10 (13)
C13—C14—H14A	109.6	O5—S2—C18	102.95 (13)

N1—C1—C2—N2	−8.8 (4)	C2—C1—N1—C12	−177.6 (2)
C9—C1—C2—N2	173.7 (2)	C9—C1—N1—C13	171.7 (2)
N1—C1—C2—C6	172.4 (2)	C2—C1—N1—C13	−5.8 (3)
C9—C1—C2—C6	−5.1 (4)	C14—C13—N1—C12	−149.1 (2)
N2—C3—C4—C5	4.9 (4)	C14—C13—N1—C1	38.9 (3)
C15—C3—C4—C5	−173.5 (2)	C4—C3—N2—C2	−0.6 (4)
C3—C4—C5—C6	−4.0 (4)	C15—C3—N2—C2	177.8 (2)
N2—C2—C6—C5	5.5 (4)	C4—C3—N2—C14	−171.0 (2)
C1—C2—C6—C5	−175.7 (2)	C15—C3—N2—C14	7.4 (3)
N2—C2—C6—C7	−173.4 (2)	C6—C2—N2—C3	−4.6 (4)
C1—C2—C6—C7	5.4 (4)	C1—C2—N2—C3	176.6 (2)
C4—C5—C6—C2	−1.3 (4)	C6—C2—N2—C14	166.3 (2)
C4—C5—C6—C7	177.6 (2)	C1—C2—N2—C14	−12.5 (3)
C2—C6—C7—C8	−1.6 (4)	C13—C14—N2—C3	−143.2 (2)
C5—C6—C7—C8	179.6 (2)	C13—C14—N2—C2	45.8 (3)
C6—C7—C8—C9	−2.6 (4)	F3—C17—S1—O2	−59.0 (2)
N1—C1—C9—C10	1.6 (4)	F1—C17—S1—O2	61.3 (2)
C2—C1—C9—C10	179.1 (2)	F2—C17—S1—O2	−179.42 (17)
N1—C1—C9—C8	−176.6 (2)	F3—C17—S1—O1	−178.89 (19)
C2—C1—C9—C8	1.0 (4)	F1—C17—S1—O1	−58.6 (2)
C7—C8—C9—C1	2.9 (4)	F2—C17—S1—O1	60.7 (2)
C7—C8—C9—C10	−175.2 (2)	F3—C17—S1—O3	61.3 (2)
C1—C9—C10—C11	−1.1 (4)	F1—C17—S1—O3	−178.36 (17)
C8—C9—C10—C11	177.0 (3)	F2—C17—S1—O3	−59.1 (2)
C9—C10—C11—C12	−0.9 (4)	F5—C18—S2—O4	178.2 (2)
C10—C11—C12—N1	2.3 (4)	F4—C18—S2—O4	−60.2 (2)
C10—C11—C12—C16	−175.7 (2)	F6—C18—S2—O4	58.9 (2)
N1—C13—C14—N2	−58.2 (3)	F5—C18—S2—O6	−62.3 (2)
C11—C12—N1—C1	−1.8 (4)	F4—C18—S2—O6	59.3 (2)
C16—C12—N1—C1	176.3 (2)	F6—C18—S2—O6	178.4 (2)
C11—C12—N1—C13	−173.3 (2)	F5—C18—S2—O5	57.5 (2)
C16—C12—N1—C13	4.8 (4)	F4—C18—S2—O5	179.1 (2)
C9—C1—N1—C12	−0.1 (4)	F6—C18—S2—O5	−61.8 (2)

Acknowledgements

The authors thank the EPSRC for funding (grant No. GR/R81459 and a PhD studentship).

References

Brian, R. C., Homer, R. F., Stubbs, J. & Jones, R. L. (1958). Nature (London), 181, 446–447. CrossRef CAS Web of Science Google Scholar
Bruker (1997). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Coe, B. J., Curati, N. R. M. & Fitzgerald, E. C. (2006). Synthesis, pp. 146–150. Web of Science CrossRef Google Scholar
Coe, B. J., Fitzgerald, E. C. & Raftery, J. (2006). Acta Cryst. E62, o4335–o4336. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hofbauer, M., Möbius, M., Knoch, F. & Benedix, R. (1996). Inorg. Chim. Acta, 247, 147–154. CSD CrossRef CAS Web of Science Google Scholar
Kim, Y.-H., Das, A., Zhang, H.-Y. & Dutta, P. K. (2005). J. Phys. Chem. B, 109, 6929–6032. Web of Science CrossRef PubMed CAS Google Scholar
Kim, Y.-H., Lee, H.-J., Dutta, P. K. & Das, A. (2003). Inorg. Chem. 42, 4215–4222. Web of Science CrossRef PubMed CAS Google Scholar
Klumpp, T., Linsenmann, M., Larson, S. L., Limoges, B. R., Bürssner, D., Krissinel, E. B., Elliott, C. M. & Steiner, U. E. (1999). J. Am. Chem. Soc. 121, 1076–1087. Web of Science CrossRef CAS Google Scholar
Nunn, I., Eisen, B., Benedix, R. & Kisch, H. (1994). Inorg. Chem. 33, 5079–5085. CrossRef CAS Web of Science Google Scholar
Ryu, C. K., Wang, R.-Y., Schmehl, R. H., Ferrere, S., Ludwikow, M., Merkert, J. W., Headford, C. E. L. & Elliott, C. M. (1992). J. Am. Chem. Soc. 114, 430–438. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Summers, L. A. (1981). The Bipyridinium Herbicides. London: Academic Press. Google Scholar
Unamuno, I., Gutiérrez-Zorrilla, J. M., Luque, A., Román, P., Lezama, L., Calvo, R. & Rojo, T. (1998). Inorg. Chem. 37, 6452–6460. Web of Science CSD CrossRef PubMed CAS Google Scholar
Vitoria, P., Beitia, J. I., Gutiérrez-Zorrilla, J. M., Sáiz, E. R., Luque, A., Insausti, M. & Blanco, J. J. (2002). Inorg. Chem. 41, 4396–4404. Web of Science CSD CrossRef PubMed CAS Google Scholar

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