2,7-Dimethyl-2,7-diazo-niapyrene bis-(hexa-fluoro-phosphate).

In the title compound, C(16)H(14)N(2) (2+)·2PF(6) (-), the 2,7-dimethyl-2,7-diaza-pyrenium (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, mol-ecules are linked into a two-dimensional lamellar framework parallel to (104) through weak C-H⋯F inter-actions.

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

C16H14N2 2+·2PF6 −

M = 524.23

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.182

S = 1.06

1756 reflections

146 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.34 e Å−3

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.

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

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

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

C16H14N22+·2PF6−	F(000) = 524
Mr = 524.23	Dx = 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

Rigaku R-AXIS RAPID diffractometer	1756 independent reflections
Radiation source: fine-focus sealed tube	1439 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 0 pixels mm-1	θmax = 25.4°, θmin = 3.0°
ω scans	h = −8→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.899, Tmax = 0.937	l = −16→16
7699 measured 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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.106P)2 + 0.7563P] where P = (Fo2 + 2Fc2)/3
1756 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.34 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.

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

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) ; (ii) .