2,7-Dimethyl-2,7-diazo­niapyrene bis­(hexa­fluoro­phosphate)

Ang, L.

doi:10.1107/S1600536811001978

organic compounds

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Volume 67| Part 2| February 2011| Page o508

doi:10.1107/S1600536811001978

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2,7-Dimethyl-2,7-diazoniapyrene bis(hexafluorophosphate)

Li Ang ^a ^*

^aCollege of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310035, People's Republic of China
^*Correspondence e-mail: liang@mail.zjgsu.edu.cn

(Received 1 December 2010; accepted 13 January 2011; online 29 January 2011)

In the title compound, C₁₆H₁₄N₂²⁺·2PF₆⁻, the 2,7-dimethyl-2,7-diazapyrenium (DM-diaz) cation lies on a crystallographic twofold rotation axes. The diaz groups are nearly coplanar, with a maximum deviation of 0.008 (3) Å. In the crystal, molecules are linked into a two-dimensional lamellar framework parallel to (104) through weak C—H⋯F interactions.

Related literature

For general background to 2,7-disubstituted diazapyrenium dications, see: Ashton et al. (1999 ); Yen et al. (2009 ); Steuerman et al. (2004 ); Lilienthal et al. (1996 ); Sindelar et al. (2005 ); Lin et al. (2006 ). For related structures, see: Blake et al. (1997 ); Dinolfo et al. (2004 ).

Experimental

Crystal data

C₁₆H₁₄N₂²⁺·2PF₆⁻
M_r = 524.23
Monoclinic, P 2₁ /n
a = 6.7654 (14) Å
b = 10.653 (2) Å
c = 13.422 (3) Å
β = 91.03 (3)°
V = 967.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.31 × 0.31 × 0.19 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.899, T_max = 0.937
7699 measured reflections
1756 independent reflections
1439 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.182
S = 1.06
1756 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯F2ⁱ	0.93	2.48	3.367 (4)	160
C7—H7⋯F4ⁱⁱ	0.93	2.51	3.418 (5)	167
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001978/bg2385sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001978/bg2385Isup2.hkl

checkCIF report

Comment top

2,7-Disubstituted diazapyrenium dications, which combine the features of pyrene, methylviologen, and nucletic acid intercalators, are charming pi-electron deficient building blocks in supramolecular chemistry (Ashton et al., 1999; Yen et al., 2009). They have been widely used as the electron-acceptors for electron-donating units such as hydroquinones and aromatic carboxylates (Steuerman et al., 2004; Lilienthal et al., 1996). Furthermore, due to their luminescence properties, they have also been as fluorescence probes for ion detection (Sindelar et al., 2005) and neurotransmition (Lin et al., 2006). Herein, we report the crystal structure of one of these disubstituted diazapyrenium dications, the N,N'-dimethyl-2,7-diazapyrenium, C₁₆H₁₄N₂.2PF₆, (DM-diaz).

The cation lies on a crystallographic twofold rotation axes; diaz groups are nearly coplanar with a maximum deviation of 0.008 (3) Å. Unlike many structures that contain diaz (Blake et al., 1997; Dinolfo et al., 2004), Dm-diaz exhibits no face-to-face pi-pi interactions between diaz molecules in the structure. C—H···F interactions are observed between the methyl groups of the DM-diaz molecules and hexafluorophoshate counterions (Table 1), forming a two-dimensional lamellar framework parallel to (101) (Figure 2).

Related literature top

For general background to 2,7-disubstituted diazapyrenium dications, see: Ashton et al. (1999); Yen et al. (2009); Steuerman et al. (2004); Lilienthal et al. (1996); Sindelar et al. (2005); Lin et al. (2006). For related structures, see: Blake et al. (1997); Dinolfo et al. (2004).

Experimental top

A solution of 2,7-diazapyrene (0.210 g, 1.03 mmol) and iodomethane (0.568 g, 4.02 mmol) in acetonitrile (15 ml) was stirred and refluxed for 3 h. After it was cooled to room temperature, a red solid was isolated on a filter and washed with ethyl ether (30 ml). The solid was dissolved with water (75 ml) and a saturated aqueous solution of NH₄PF₆ (2.44 g, 15.0 mmol) was added until no further precipitate was observed. The red solid was isolated on a filter, washed with water and dried under vacuum to afford the product (0.423 g, 78.4%). Red crystals were obtained by vapor diffusion of isopropyl ether into an acetonitrile solution over a period of 5 d. ¹H NMR (500 MHz, CD₃CN, 295 K) δ (p.p.m.) 9.88 (4H,s), 8.85 (4H, s), 5.14 (4H, t, J = 5.2 Hz), 3.45 (4H, m), 3.45 (2H, t, J = 5.5 Hz).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the title compound. The dispalcement ellipsoids are drawn at 30% probability level. Symmetry code: (A) 2-x, 1-y, 1-z
	Fig. 2. The two-dimensional layer of the compound, parallel to (101).

2,7-Dimethyl-2,7-diazoniapyrene bis(hexafluorophosphate) top

Crystal data top

C₁₆H₁₄N₂²⁺·2PF₆⁻	F(000) = 524
M_r = 524.23	D_x = 1.800 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6424 reflections
a = 6.7654 (14) Å	θ = 3.0–27.5°
b = 10.653 (2) Å	µ = 0.35 mm⁻¹
c = 13.422 (3) Å	T = 293 K
β = 91.03 (3)°	Block, yellow
V = 967.2 (3) Å³	0.31 × 0.31 × 0.19 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1756 independent reflections
Radiation source: fine-focus sealed tube	1439 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 0 pixels mm^-1	θ_max = 25.4°, θ_min = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
T_min = 0.899, T_max = 0.937	l = −16→16
7699 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.106P)² + 0.7563P] where P = (F_o² + 2F_c²)/3
1756 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₆H₁₄N₂²⁺·2PF₆⁻	V = 967.2 (3) Å³
M_r = 524.23	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7654 (14) Å	µ = 0.35 mm⁻¹
b = 10.653 (2) Å	T = 293 K
c = 13.422 (3) Å	0.31 × 0.31 × 0.19 mm
β = 91.03 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1756 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1439 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.937	R_int = 0.021
7699 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 1.06	Δρ_max = 0.48 e Å⁻³
1756 reflections	Δρ_min = −0.34 e Å⁻³
146 parameters

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.

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	0.73691 (12)	0.87716 (8)	0.67479 (6)	0.0486 (4)
F1	0.7852 (5)	0.9813 (3)	0.7544 (3)	0.1277 (13)
F2	0.7768 (4)	0.7779 (3)	0.7596 (2)	0.1015 (10)
F3	0.5103 (3)	0.8793 (2)	0.7022 (2)	0.0842 (8)
F4	0.7012 (5)	0.9817 (4)	0.5943 (3)	0.1329 (14)
F5	0.9644 (3)	0.8750 (3)	0.6478 (2)	0.0953 (10)
F6	0.6946 (4)	0.7712 (3)	0.5961 (2)	0.1071 (11)
N1	1.1916 (4)	0.2419 (2)	0.61997 (19)	0.0458 (6)
C1	1.0682 (4)	0.6661 (3)	0.4751 (2)	0.0399 (7)
C2	1.2564 (4)	0.6724 (3)	0.5268 (2)	0.0459 (7)
H2	1.3272	0.7472	0.5275	0.055*
C3	1.3308 (4)	0.5710 (3)	0.5740 (2)	0.0463 (7)
H3	1.4527	0.5765	0.6068	0.056*
C4	1.2250 (4)	0.4551 (3)	0.5743 (2)	0.0390 (7)
C5	1.0387 (4)	0.4467 (2)	0.52485 (19)	0.0360 (6)
C6	1.2952 (4)	0.3482 (3)	0.6213 (2)	0.0459 (7)
H6	1.4170	0.3505	0.6545	0.055*
C7	1.0142 (4)	0.2319 (3)	0.5739 (2)	0.0448 (7)
H7	0.9465	0.1560	0.5750	0.054*
C8	1.2764 (7)	0.1282 (3)	0.6680 (3)	0.0680 (11)
H8A	1.1728	0.0810	0.6984	0.102*
H8C	1.3721	0.1526	0.7180	0.102*
H8B	1.3392	0.0774	0.6187	0.102*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0456 (6)	0.0520 (6)	0.0482 (6)	−0.0031 (3)	−0.0017 (4)	−0.0009 (4)
F1	0.142 (3)	0.105 (2)	0.136 (3)	−0.007 (2)	−0.003 (2)	−0.068 (2)
F2	0.097 (2)	0.105 (2)	0.103 (2)	0.0185 (16)	−0.0030 (16)	0.0420 (17)
F3	0.0548 (14)	0.105 (2)	0.0938 (18)	0.0116 (12)	0.0153 (12)	0.0123 (14)
F4	0.109 (2)	0.150 (3)	0.140 (3)	−0.012 (2)	−0.008 (2)	0.093 (2)
F5	0.0494 (13)	0.125 (2)	0.112 (2)	−0.0215 (13)	0.0103 (13)	−0.0286 (17)
F6	0.0775 (16)	0.143 (3)	0.101 (2)	−0.0446 (17)	0.0222 (15)	−0.0672 (19)
N1	0.0497 (14)	0.0464 (14)	0.0414 (13)	0.0030 (11)	0.0029 (11)	0.0041 (11)
C1	0.0359 (14)	0.0422 (15)	0.0418 (15)	−0.0054 (12)	0.0052 (12)	−0.0036 (12)
C2	0.0366 (15)	0.0449 (17)	0.0561 (19)	−0.0096 (12)	−0.0002 (14)	−0.0050 (14)
C3	0.0322 (14)	0.0558 (18)	0.0509 (17)	−0.0075 (13)	−0.0040 (13)	−0.0064 (14)
C4	0.0323 (14)	0.0464 (16)	0.0381 (14)	−0.0014 (11)	−0.0005 (11)	−0.0040 (12)
C5	0.0325 (14)	0.0415 (15)	0.0341 (14)	−0.0027 (11)	0.0043 (11)	−0.0053 (11)
C6	0.0409 (16)	0.0567 (18)	0.0399 (16)	0.0017 (13)	−0.0031 (13)	−0.0028 (13)
C7	0.0461 (17)	0.0434 (16)	0.0451 (16)	−0.0035 (13)	0.0076 (14)	−0.0001 (13)
C8	0.078 (3)	0.057 (2)	0.068 (2)	0.0077 (18)	−0.015 (2)	0.0186 (18)

Geometric parameters (Å, º) top

P1—F4	1.567 (3)	C2—C3	1.346 (4)
P1—F6	1.568 (2)	C2—H2	0.9300
P1—F1	1.570 (3)	C3—C4	1.427 (4)
P1—F2	1.574 (3)	C3—H3	0.9300
P1—F3	1.583 (2)	C4—C6	1.382 (4)
P1—F5	1.587 (2)	C4—C5	1.417 (4)
N1—C6	1.332 (4)	C5—C5ⁱ	1.413 (5)
N1—C7	1.344 (4)	C6—H6	0.9300
N1—C8	1.483 (4)	C7—H7	0.9300
C1—C7ⁱ	1.382 (4)	C8—H8A	0.9600
C1—C5ⁱ	1.402 (4)	C8—H8C	0.9600
C1—C2	1.440 (4)	C8—H8B	0.9600

F4—P1—F6	91.3 (2)	C1—C2—H2	119.7
F4—P1—F1	89.7 (2)	C2—C3—C4	120.8 (3)
F6—P1—F1	178.30 (18)	C2—C3—H3	119.6
F4—P1—F2	176.9 (2)	C4—C3—H3	119.6
F6—P1—F2	91.8 (2)	C6—C4—C5	117.2 (3)
F1—P1—F2	87.2 (2)	C6—C4—C3	123.1 (3)
F4—P1—F3	90.70 (16)	C5—C4—C3	119.7 (3)
F6—P1—F3	90.07 (15)	C1ⁱ—C5—C5ⁱ	120.2 (3)
F1—P1—F3	91.28 (17)	C1ⁱ—C5—C4	120.6 (3)
F2—P1—F3	89.74 (15)	C5ⁱ—C5—C4	119.3 (3)
F4—P1—F5	89.51 (18)	N1—C6—C4	121.2 (3)
F6—P1—F5	90.11 (14)	N1—C6—H6	119.4
F1—P1—F5	88.54 (17)	C4—C6—H6	119.4
F2—P1—F5	90.04 (17)	N1—C7—C1ⁱ	120.4 (3)
F3—P1—F5	179.73 (16)	N1—C7—H7	119.8
C6—N1—C7	122.6 (3)	C1ⁱ—C7—H7	119.8
C6—N1—C8	119.3 (3)	N1—C8—H8A	109.5
C7—N1—C8	118.1 (3)	N1—C8—H8C	109.5
C7ⁱ—C1—C5ⁱ	118.0 (3)	H8A—C8—H8C	109.5
C7ⁱ—C1—C2	122.6 (3)	N1—C8—H8B	109.5
C5ⁱ—C1—C2	119.4 (3)	H8A—C8—H8B	109.5
C3—C2—C1	120.6 (3)	H8C—C8—H8B	109.5
C3—C2—H2	119.7

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F2ⁱⁱ	0.93	2.48	3.367 (4)	160
C7—H7···F4ⁱⁱⁱ	0.93	2.51	3.418 (5)	167

Symmetry codes: (ii) −x+5/2, y−1/2, −z+3/2; (iii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₂²⁺·2PF₆⁻
M_r	524.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.7654 (14), 10.653 (2), 13.422 (3)
β (°)	91.03 (3)
V (Å³)	967.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.31 × 0.31 × 0.19

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.899, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	7699, 1756, 1439
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.182, 1.06
No. of reflections	1756
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.34

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F2ⁱ	0.93	2.48	3.367 (4)	160
C7—H7···F4ⁱⁱ	0.93	2.51	3.418 (5)	167

Symmetry codes: (i) −x+5/2, y−1/2, −z+3/2; (ii) x, y−1, z.

Acknowledgements

This work was supported by the fund of Zhejiang Gongshang University (No. 10–3).

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