3,3′-Dicyclo­pentyl-1,1′-(1,3-phenyl­enedimethyl­ene)dibenzimidazol-1-ium bis­(hexa­fluoro­phosphate)

Haque, R.A.; Nasri, S.F.; Rosli, M.M.; Fun, H.-K.

doi:10.1107/S160053681202274X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1868

doi:10.1107/S160053681202274X

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3,3′-Dicyclopentyl-1,1′-(1,3-phenylenedimethylene)dibenzimidazol-1-ium bis(hexafluorophosphate)

Rosenani A. Haque,^a S. Fatimah Nasri,^a Mohd Mustaqim Rosli ^b and Hoong-Kun Fun ^b ^*‡

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 7 May 2012; accepted 18 May 2012; online 23 May 2012)

In the title compound, C₃₂H₃₆N₄²⁺·2PF₆⁻, the cation and the anions each have crystallographic twofold rotation symmetry. The benzimidazole ring is almost planar [r.m.s. deviation = 0.0161 (1) Å] and makes a dihedral angle of 5.77 (4)° with its symmetry-related component and a dihedral angle of 80.96 (5)° with the central benzene ring. The cyclopentyl ring adopts a half-chair conformation. In the crystal, molecules are linked into a three-dimensional network through C—H⋯F hydrogen bonds. A C—H⋯π interaction is also observed.

Related literature

For the biological activity of benzimidazole, see: Shaharyar et al. (2012 ); Mohan et al. (2011 ). For related structures, see: Haque et al. (2011 , 2012 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₃₂H₃₆N₄²⁺·2PF₆⁻
M_r = 766.59
Orthorhombic, C 222₁
a = 7.0699 (1) Å
b = 20.4852 (3) Å
c = 22.5416 (3) Å
V = 3264.66 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.44 × 0.13 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.903, T_max = 0.974
19037 measured reflections
4758 independent reflections
4407 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.078
S = 1.05
4758 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 2086 Friedel pairs
Flack parameter: 0.02 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯F3ⁱ	0.95	2.44	3.3814 (18)	171
C5—H5B⋯F4ⁱⁱ	0.99	2.41	3.2670 (17)	145
C8—H8A⋯F2ⁱⁱⁱ	0.95	2.46	3.3912 (18)	167
C12—H12A⋯F4ⁱⁱ	0.95	2.42	3.2252 (17)	142
C13—H13A⋯F2^iv	1.00	2.51	3.4090 (18)	150
C13—H13A⋯F3^iv	1.00	2.31	3.2124 (17)	149
C9—H9A⋯Cg1^iv	0.95	2.79	3.6416 (15)	149
Symmetry codes: (i) x, -y, -z+1; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681202274X/rz2756sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202274X/rz2756Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202274X/rz2756Isup3.cml

checkCIF report

Comment top

Benzimidazole, a heterocyclic aromatic organic compound, has a wide variety of biological activities (Shaharyar et al., 2012; Mohan et al., 2011). Previously, we have reported the crystal structures of benzimidazole with various substitutions (Haque et al., 2011, 2012). In this report, we describe the crystal structure of a meta-xylyl linked bis-benzimidazolium salt with cyclopentyl substitution.

All parameters in the title compound (Fig. 1) are within normal ranges. The complete molecule, as well as the anions, is generated by a crystallographic twofold axis. The benzimidazole (N1—N2/C6—C12) ring is planar with the r.m.s. 0.0161 (1) Å. It makes a dihedral angle of 5.77 (4)° with its symmetry-related component and of 80.96 (5)° with the central benzene ring (C1—C4/C2A—C3A). The cyclopentyl ring adopts a half chair conformation with puckering parameters Q = 0.4256 (18) Å and ϕ = 344.9 (3)° (Cremer & Pople, 1975).

In the crystal structure (Fig. 2), the molecules are linked into a three-dimensional network through intermolecular C—H···F hydrogen bonds and C—H···π interactions involving the centroid of the C6—C11 ring (Table 1).

Related literature top

For the biological activity of benzimidazole, see: Shaharyar et al. (2012); Mohan et al. (2011). For related structures, see: Haque et al. (2011, 2012). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

To a solution of 1,3-(bromomethyl)benzene (2.64 g, 0.01 mol) in 50 ml of 1,4-dioxane, 1-cyclopentyl-1H-benzolimidazole (3.73 g, 0.02 mol) was added. The mixture was refluxed at 373 K for 24 h. The resulting brown thick liquid product was decanted, washed with fresh 1,4-dioxane (3 × 5 ml) and converted directly to its hexafluorophosphate counterpart by metathesis reaction using KPF₆ (3.60 g, 0.02 mol) in 40 ml of methanol/water. The white precipitate was collected, washed with fresh methanol to give the title product as a white solid (4.66 g, 97%). M.p. 518–519 K. Crystals suitable for X-ray diffraction studies were obtained by slow evaporation of the salt solution in a mixture of acetonitrile/methanol (1:1 v/v) at ambient temperature.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. Hydrogen atoms are shown as spheres of arbitrary radius. Atoms with suffix A, B and C are generated by the symmetry operators (-x, y, 1/2-z), (x, -y, 1-z) and (-x, y, 3/2-z), respectively.
	Fig. 2. The crystal packing of the title compound. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding interactions have been omitted for clarity.

3,3'-Dicyclopentyl-1,1'-(1,3-phenylenedimethylene)dibenzimidazol-1-ium bis(hexafluorophosphate) top

Crystal data top

C₃₂H₃₆N₄²⁺·2PF₆⁻	F(000) = 1576
M_r = 766.59	D_x = 1.560 Mg m⁻³
Orthorhombic, C222₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 9943 reflections
a = 7.0699 (1) Å	θ = 2.2–29.9°
b = 20.4852 (3) Å	µ = 0.23 mm⁻¹
c = 22.5416 (3) Å	T = 100 K
V = 3264.66 (8) Å³	Block, colourless
Z = 4	0.44 × 0.13 × 0.11 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4758 independent reflections
Radiation source: fine-focus sealed tube	4407 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.903, T_max = 0.974	k = −28→28
19037 measured reflections	l = −28→31

Refinement top

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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0411P)² + 1.0871P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4758 reflections	Δρ_max = 0.29 e Å⁻³
228 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2086 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (7)

Crystal data top

C₃₂H₃₆N₄²⁺·2PF₆⁻	V = 3264.66 (8) Å³
M_r = 766.59	Z = 4
Orthorhombic, C222₁	Mo Kα radiation
a = 7.0699 (1) Å	µ = 0.23 mm⁻¹
b = 20.4852 (3) Å	T = 100 K
c = 22.5416 (3) Å	0.44 × 0.13 × 0.11 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4758 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4407 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.974	R_int = 0.024
19037 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.078	Δρ_max = 0.29 e Å⁻³
S = 1.05	Δρ_min = −0.24 e Å⁻³
4758 reflections	Absolute structure: Flack (1983), 2086 Friedel pairs
228 parameters	Absolute structure parameter: 0.02 (7)
0 restraints

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.12643 (8)	0.0000	0.5000	0.01579 (10)
F1	−0.03216 (16)	0.05234 (5)	0.48352 (4)	0.0333 (2)
F2	0.28761 (15)	0.05230 (5)	0.48369 (4)	0.0313 (2)
F3	0.12649 (14)	0.02573 (5)	0.56726 (4)	0.02558 (19)
P2	0.0000	0.20928 (3)	0.7500	0.01858 (11)
F4	0.03085 (15)	0.26421 (5)	0.79953 (4)	0.0304 (2)
F5	−0.03160 (16)	0.15392 (5)	0.70063 (4)	0.0331 (2)
F6	0.22344 (14)	0.20932 (5)	0.73648 (4)	0.0307 (2)
N1	0.01439 (18)	0.21030 (6)	0.37157 (5)	0.0166 (2)
N2	−0.04694 (17)	0.31380 (6)	0.38710 (5)	0.0158 (2)
C1	0.0000	0.01437 (9)	0.2500	0.0217 (4)
H1A	0.0000	−0.0320	0.2500	0.026*
C2	0.0497 (2)	0.04841 (7)	0.30090 (7)	0.0187 (3)
H2A	0.0830	0.0252	0.3359	0.022*
C3	0.0511 (2)	0.11646 (6)	0.30090 (6)	0.0155 (3)
C4	0.0000	0.15040 (9)	0.2500	0.0171 (4)
H4A	0.0000	0.1968	0.2500	0.020*
C5	0.1218 (2)	0.15116 (6)	0.35629 (6)	0.0184 (3)
H5A	0.1158	0.1204	0.3901	0.022*
H5B	0.2561	0.1632	0.3504	0.022*
C6	−0.1642 (2)	0.21287 (7)	0.39812 (6)	0.0159 (3)
C7	−0.2882 (2)	0.16395 (7)	0.41598 (7)	0.0203 (3)
H7A	−0.2614	0.1191	0.4095	0.024*
C8	−0.4523 (2)	0.18423 (7)	0.44364 (7)	0.0215 (3)
H8A	−0.5404	0.1524	0.4568	0.026*
C9	−0.4927 (2)	0.25100 (7)	0.45287 (6)	0.0194 (3)
H9A	−0.6077	0.2628	0.4718	0.023*
C10	−0.3694 (2)	0.29965 (7)	0.43506 (6)	0.0168 (3)
H10A	−0.3966	0.3446	0.4411	0.020*
C11	−0.2030 (2)	0.27901 (6)	0.40778 (6)	0.0157 (3)
C12	0.0780 (2)	0.27128 (7)	0.36572 (6)	0.0173 (3)
H12A	0.1962	0.2828	0.3486	0.021*
C13	−0.0262 (2)	0.38548 (6)	0.38878 (7)	0.0187 (3)
H13A	−0.1242	0.4034	0.4163	0.022*
C14	−0.0516 (3)	0.41777 (8)	0.32852 (8)	0.0328 (4)
H14A	−0.1872	0.4213	0.3181	0.039*
H14B	0.0147	0.3929	0.2971	0.039*
C15	0.0376 (3)	0.48588 (8)	0.33678 (10)	0.0377 (5)
H15A	0.1187	0.4970	0.3024	0.045*
H15B	−0.0620	0.5196	0.3407	0.045*
C16	0.1564 (2)	0.48203 (7)	0.39385 (8)	0.0258 (3)
H16A	0.2848	0.4998	0.3871	0.031*
H16B	0.0956	0.5070	0.4262	0.031*
C17	0.1659 (2)	0.40913 (7)	0.40946 (7)	0.0233 (3)
H17A	0.2696	0.3870	0.3879	0.028*
H17B	0.1828	0.4024	0.4526	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0180 (2)	0.0139 (2)	0.0155 (2)	0.000	0.000	0.00104 (18)
F1	0.0360 (6)	0.0354 (5)	0.0287 (5)	0.0206 (4)	−0.0024 (4)	−0.0028 (4)
F2	0.0348 (6)	0.0286 (5)	0.0304 (5)	−0.0119 (4)	0.0112 (4)	0.0012 (4)
F3	0.0298 (5)	0.0311 (4)	0.0158 (4)	−0.0089 (4)	0.0008 (4)	−0.0032 (4)
P2	0.0195 (3)	0.0204 (2)	0.0159 (2)	0.000	−0.0036 (2)	0.000
F4	0.0330 (6)	0.0316 (5)	0.0266 (5)	0.0000 (4)	−0.0041 (4)	−0.0115 (4)
F5	0.0414 (6)	0.0304 (5)	0.0276 (5)	−0.0014 (5)	−0.0082 (5)	−0.0105 (4)
F6	0.0202 (5)	0.0419 (5)	0.0300 (6)	0.0038 (4)	−0.0009 (4)	−0.0035 (4)
N1	0.0196 (6)	0.0151 (5)	0.0152 (5)	−0.0003 (5)	0.0004 (5)	−0.0011 (4)
N2	0.0162 (6)	0.0144 (5)	0.0168 (6)	−0.0026 (4)	0.0024 (4)	−0.0011 (4)
C1	0.0268 (11)	0.0110 (8)	0.0273 (11)	0.000	−0.0015 (9)	0.000
C2	0.0206 (7)	0.0158 (6)	0.0197 (7)	0.0016 (5)	0.0000 (6)	0.0027 (5)
C3	0.0161 (6)	0.0135 (6)	0.0169 (6)	0.0001 (5)	0.0011 (5)	−0.0018 (5)
C4	0.0208 (9)	0.0116 (8)	0.0188 (9)	0.000	0.0011 (8)	0.000
C5	0.0219 (7)	0.0146 (6)	0.0186 (7)	0.0048 (6)	−0.0030 (6)	−0.0007 (5)
C6	0.0186 (7)	0.0180 (6)	0.0111 (6)	−0.0010 (5)	−0.0022 (5)	0.0007 (5)
C7	0.0241 (8)	0.0165 (6)	0.0202 (7)	−0.0031 (5)	−0.0041 (6)	0.0024 (5)
C8	0.0221 (7)	0.0226 (7)	0.0199 (7)	−0.0079 (6)	−0.0005 (6)	0.0058 (6)
C9	0.0168 (7)	0.0252 (7)	0.0163 (6)	−0.0033 (6)	0.0004 (6)	0.0029 (5)
C10	0.0183 (6)	0.0175 (6)	0.0145 (6)	−0.0002 (5)	0.0002 (5)	0.0004 (5)
C11	0.0194 (7)	0.0156 (6)	0.0121 (6)	−0.0036 (5)	−0.0014 (5)	0.0002 (5)
C12	0.0190 (7)	0.0182 (6)	0.0149 (6)	−0.0012 (5)	0.0012 (5)	−0.0004 (5)
C13	0.0191 (7)	0.0116 (5)	0.0253 (7)	−0.0020 (5)	0.0043 (6)	−0.0021 (5)
C14	0.0383 (10)	0.0226 (8)	0.0376 (10)	−0.0044 (7)	−0.0151 (8)	0.0105 (7)
C15	0.0298 (9)	0.0254 (8)	0.0578 (13)	−0.0078 (7)	−0.0142 (9)	0.0182 (8)
C16	0.0223 (8)	0.0176 (7)	0.0376 (9)	−0.0050 (5)	0.0037 (7)	−0.0022 (6)
C17	0.0241 (8)	0.0192 (7)	0.0267 (8)	−0.0060 (6)	−0.0051 (6)	−0.0001 (6)

Geometric parameters (Å, º) top

P1—F1	1.5951 (10)	C5—H5A	0.9900
P1—F1ⁱ	1.5952 (10)	C5—H5B	0.9900
P1—F3	1.6051 (9)	C6—C7	1.391 (2)
P1—F3ⁱ	1.6051 (9)	C6—C11	1.3993 (19)
P1—F2	1.6067 (10)	C7—C8	1.381 (2)
P1—F2ⁱ	1.6067 (10)	C7—H7A	0.9500
P2—F4ⁱⁱ	1.6002 (10)	C8—C9	1.413 (2)
P2—F4	1.6002 (10)	C8—H8A	0.9500
P2—F5	1.6046 (10)	C9—C10	1.384 (2)
P2—F5ⁱⁱ	1.6046 (10)	C9—H9A	0.9500
P2—F6	1.6088 (10)	C10—C11	1.393 (2)
P2—F6ⁱⁱ	1.6088 (10)	C10—H10A	0.9500
N1—C12	1.3342 (18)	C12—H12A	0.9500
N1—C6	1.3981 (19)	C13—C17	1.515 (2)
N1—C5	1.4707 (17)	C13—C14	1.522 (2)
N2—C12	1.3307 (18)	C13—H13A	1.0000
N2—C11	1.3935 (18)	C14—C15	1.542 (2)
N2—C13	1.4762 (17)	C14—H14A	0.9900
C1—C2ⁱⁱⁱ	1.3879 (18)	C14—H14B	0.9900
C1—C2	1.3879 (18)	C15—C16	1.538 (3)
C1—H1A	0.9500	C15—H15A	0.9900
C2—C3	1.3942 (19)	C15—H15B	0.9900
C2—H2A	0.9500	C16—C17	1.536 (2)
C3—C4	1.3894 (17)	C16—H16A	0.9900
C3—C5	1.5210 (19)	C16—H16B	0.9900
C4—C3ⁱⁱⁱ	1.3894 (17)	C17—H17A	0.9900
C4—H4A	0.9500	C17—H17B	0.9900

F1—P1—F1ⁱ	90.68 (9)	H5A—C5—H5B	107.6
F1—P1—F3	89.97 (5)	C7—C6—N1	131.74 (13)
F1ⁱ—P1—F3	90.05 (5)	C7—C6—C11	121.94 (14)
F1—P1—F3ⁱ	90.05 (5)	N1—C6—C11	106.27 (12)
F1ⁱ—P1—F3ⁱ	89.97 (5)	C8—C7—C6	116.32 (13)
F3—P1—F3ⁱ	179.97 (8)	C8—C7—H7A	121.8
F1—P1—F2	89.83 (6)	C6—C7—H7A	121.8
F1ⁱ—P1—F2	179.47 (7)	C7—C8—C9	121.84 (14)
F3—P1—F2	89.83 (5)	C7—C8—H8A	119.1
F3ⁱ—P1—F2	90.15 (5)	C9—C8—H8A	119.1
F1—P1—F2ⁱ	179.47 (7)	C10—C9—C8	121.82 (14)
F1ⁱ—P1—F2ⁱ	89.83 (6)	C10—C9—H9A	119.1
F3—P1—F2ⁱ	90.15 (5)	C8—C9—H9A	119.1
F3ⁱ—P1—F2ⁱ	89.83 (5)	C9—C10—C11	116.20 (12)
F2—P1—F2ⁱ	89.66 (8)	C9—C10—H10A	121.9
F4ⁱⁱ—P2—F4	90.62 (8)	C11—C10—H10A	121.9
F4ⁱⁱ—P2—F5	89.66 (5)	C10—C11—N2	131.36 (12)
F4—P2—F5	179.64 (6)	C10—C11—C6	121.87 (13)
F4ⁱⁱ—P2—F5ⁱⁱ	179.64 (6)	N2—C11—C6	106.74 (12)
F4—P2—F5ⁱⁱ	89.66 (5)	N2—C12—N1	110.70 (13)
F5—P2—F5ⁱⁱ	90.05 (8)	N2—C12—H12A	124.6
F4ⁱⁱ—P2—F6	90.07 (6)	N1—C12—H12A	124.6
F4—P2—F6	89.89 (6)	N2—C13—C17	114.52 (12)
F5—P2—F6	90.33 (6)	N2—C13—C14	113.44 (12)
F5ⁱⁱ—P2—F6	89.72 (6)	C17—C13—C14	103.97 (13)
F4ⁱⁱ—P2—F6ⁱⁱ	89.88 (6)	N2—C13—H13A	108.2
F4—P2—F6ⁱⁱ	90.07 (6)	C17—C13—H13A	108.2
F5—P2—F6ⁱⁱ	89.71 (6)	C14—C13—H13A	108.2
F5ⁱⁱ—P2—F6ⁱⁱ	90.33 (6)	C13—C14—C15	103.71 (14)
F6—P2—F6ⁱⁱ	179.94 (9)	C13—C14—H14A	111.0
C12—N1—C6	108.13 (12)	C15—C14—H14A	111.0
C12—N1—C5	125.04 (13)	C13—C14—H14B	111.0
C6—N1—C5	126.70 (12)	C15—C14—H14B	111.0
C12—N2—C11	108.16 (11)	H14A—C14—H14B	109.0
C12—N2—C13	126.47 (12)	C16—C15—C14	106.14 (13)
C11—N2—C13	125.37 (12)	C16—C15—H15A	110.5
C2ⁱⁱⁱ—C1—C2	119.68 (17)	C14—C15—H15A	110.5
C2ⁱⁱⁱ—C1—H1A	120.2	C16—C15—H15B	110.5
C2—C1—H1A	120.2	C14—C15—H15B	110.5
C1—C2—C3	120.28 (14)	H15A—C15—H15B	108.7
C1—C2—H2A	119.9	C17—C16—C15	105.39 (13)
C3—C2—H2A	119.9	C17—C16—H16A	110.7
C4—C3—C2	119.91 (13)	C15—C16—H16A	110.7
C4—C3—C5	121.97 (12)	C17—C16—H16B	110.7
C2—C3—C5	118.01 (12)	C15—C16—H16B	110.7
C3ⁱⁱⁱ—C4—C3	119.95 (17)	H16A—C16—H16B	108.8
C3ⁱⁱⁱ—C4—H4A	120.0	C13—C17—C16	101.60 (12)
C3—C4—H4A	120.0	C13—C17—H17A	111.5
N1—C5—C3	114.05 (12)	C16—C17—H17A	111.5
N1—C5—H5A	108.7	C13—C17—H17B	111.5
C3—C5—H5A	108.7	C16—C17—H17B	111.5
N1—C5—H5B	108.7	H17A—C17—H17B	109.3
C3—C5—H5B	108.7

C2ⁱⁱⁱ—C1—C2—C3	−0.43 (10)	C12—N2—C11—C6	0.54 (16)
C1—C2—C3—C4	0.9 (2)	C13—N2—C11—C6	−179.62 (13)
C1—C2—C3—C5	−175.19 (12)	C7—C6—C11—C10	−1.0 (2)
C2—C3—C4—C3ⁱⁱⁱ	−0.43 (10)	N1—C6—C11—C10	−178.56 (12)
C5—C3—C4—C3ⁱⁱⁱ	175.47 (15)	C7—C6—C11—N2	177.31 (13)
C12—N1—C5—C3	−108.17 (16)	N1—C6—C11—N2	−0.29 (15)
C6—N1—C5—C3	76.47 (17)	C11—N2—C12—N1	−0.60 (17)
C4—C3—C5—N1	42.77 (18)	C13—N2—C12—N1	179.57 (13)
C2—C3—C5—N1	−141.25 (14)	C6—N1—C12—N2	0.41 (16)
C12—N1—C6—C7	−177.33 (15)	C5—N1—C12—N2	−175.68 (13)
C5—N1—C6—C7	−1.3 (2)	C12—N2—C13—C17	−44.6 (2)
C12—N1—C6—C11	−0.06 (15)	C11—N2—C13—C17	135.57 (14)
C5—N1—C6—C11	175.94 (13)	C12—N2—C13—C14	74.5 (2)
N1—C6—C7—C8	177.12 (14)	C11—N2—C13—C14	−105.29 (17)
C11—C6—C7—C8	0.2 (2)	N2—C13—C14—C15	−162.32 (14)
C6—C7—C8—C9	0.5 (2)	C17—C13—C14—C15	−37.29 (18)
C7—C8—C9—C10	−0.5 (2)	C13—C14—C15—C16	15.5 (2)
C8—C9—C10—C11	−0.3 (2)	C14—C15—C16—C17	11.4 (2)
C9—C10—C11—N2	−176.85 (14)	N2—C13—C17—C16	168.57 (13)
C9—C10—C11—C6	1.0 (2)	C14—C13—C17—C16	44.24 (15)
C12—N2—C11—C10	178.59 (15)	C15—C16—C17—C13	−33.95 (17)
C13—N2—C11—C10	−1.6 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F3ⁱ	0.95	2.44	3.3814 (18)	171
C5—H5B···F4^iv	0.99	2.41	3.2670 (17)	145
C8—H8A···F2^v	0.95	2.46	3.3912 (18)	167
C12—H12A···F4^iv	0.95	2.42	3.2252 (17)	142
C13—H13A···F2^vi	1.00	2.51	3.4090 (18)	150
C13—H13A···F3^vi	1.00	2.31	3.2124 (17)	149
C9—H9A···Cg1^vi	0.95	2.79	3.6416 (15)	149

Symmetry codes: (i) x, −y, −z+1; (iv) −x+1/2, −y+1/2, z−1/2; (v) x−1, y, z; (vi) x−1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₃₂H₃₆N₄²⁺·2PF₆⁻
M_r	766.59
Crystal system, space group	Orthorhombic, C222₁
Temperature (K)	100
a, b, c (Å)	7.0699 (1), 20.4852 (3), 22.5416 (3)
V (Å³)	3264.66 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.44 × 0.13 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.903, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	19037, 4758, 4407
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.078, 1.05
No. of reflections	4758
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24
Absolute structure	Flack (1983), 2086 Friedel pairs
Absolute structure parameter	0.02 (7)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F3ⁱ	0.9500	2.4400	3.3814 (18)	171.00
C5—H5B···F4ⁱⁱ	0.9900	2.4100	3.2670 (17)	145.00
C8—H8A···F2ⁱⁱⁱ	0.9500	2.4600	3.3912 (18)	167.00
C12—H12A···F4ⁱⁱ	0.9500	2.4200	3.2252 (17)	142.00
C13—H13A···F2^iv	1.0000	2.5100	3.4090 (18)	150.00
C13—H13A···F3^iv	1.0000	2.3100	3.2124 (17)	149.00
C9—H9A···Cg1^iv	0.95	2.7900	3.6416 (15)	149.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

RAH and SFN thank Universiti Sains Malaysia (USM) for the short-term grant (304/PKIMIA/6311123) and RU grants (1001/PKIMIA/811157 and 1001/PKIMIA/813023). HKF thanks USM for the Research University Grant No. 1001/PFIZIK/811160.

References

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