4,4'-Dimethyl-1,1'-(p-phenyl-enedimethyl-ene)dipyridinium bis-[7,7,8,8-tetra-cyano-quinodimethanide(1-)].

In the title salt, C(20)H(22)N(2) (2+)·2C(12)H(4)N(4) (-), the cations and anions stack along the b axis into segregated columns. In the cation, which has a crystallographically imposed centre of symmetry, the dihedral angle between the benzene and pyridine rings is 89.14 (4)°. Centrosymmetrically related anions form dimers by π-π stacking inter-actions, with centroid-centroid separations of 3.874 (4) Å. The crystal packing is stabilized by inter-columnar C-H⋯N hydrogen bonds.

Related literature

For general background to the planar organic mol­ecule 7,7,8,8-tetra­cyano­quinodimethane, see: Alonso et al. (2005 ▶); Madalan et al. (2002 ▶); Liu et al. (2008 ▶). For the role played by the size and shape of the counter-cations in determining the ground-state electronic properties of the resulting materials, see: Ren, Meng et al. (2002 ▶); Ren, et al. (2003 ▶); Ren, Chen et al. (2002 ▶). For related structures, see: Liu et al. (2005 ▶).

Experimental

Crystal data

C20H22N2 2+·2C12H4N4 −

M = 698.78

Triclinic,

a = 8.5904 (12) Å

b = 8.6786 (11) Å

c = 13.3016 (17) Å

α = 101.558 (2)°

β = 106.134 (2)°

γ = 97.906 (2)°

V = 913.4 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.24 × 0.22 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.981, T max = 0.988

6854 measured reflections

3353 independent reflections

2243 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.126

S = 1.00

3353 reflections

245 parameters

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017113/rz2446sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017113/rz2446Isup2.hkl

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

C20H22N22+·2C12H4N4−	Z = 1
Mr = 698.78	F(000) = 364
Triclinic, P1	Dx = 1.270 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5904 (12) Å	Cell parameters from 2212 reflections
b = 8.6786 (11) Å	θ = 2.5–26.4°
c = 13.3016 (17) Å	µ = 0.08 mm−1
α = 101.558 (2)°	T = 293 K
β = 106.134 (2)°	Block, dark green
γ = 97.906 (2)°	0.24 × 0.22 × 0.16 mm
V = 913.4 (2) Å3

Bruker SMART APEX CCD area-detector diffractometer	3353 independent reflections
Radiation source: sealed tube	2243 reflections with I > 2σ(I)
graphite	Rint = 0.023
phi and ω scans	θmax = 25.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
Tmin = 0.981, Tmax = 0.988	k = −10→10
6854 measured reflections	l = −16→15

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0561P)2 + 0.1398P] where P = (Fo2 + 2Fc2)/3
3353 reflections	(Δ/σ)max = 0.036
245 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
C1	0.3619 (2)	0.1249 (2)	−0.12031 (15)	0.0513 (5)
C2	0.1730 (3)	0.2868 (2)	−0.18890 (17)	0.0594 (5)
C3	0.2953 (2)	0.2639 (2)	−0.09960 (15)	0.0505 (5)
C4	0.3415 (2)	0.3713 (2)	0.00302 (15)	0.0464 (4)
C5	0.4625 (2)	0.3502 (2)	0.09308 (15)	0.0482 (5)
H5	0.5125	0.2620	0.0849	0.058*
C6	0.5072 (2)	0.4564 (2)	0.19137 (15)	0.0502 (5)
H6	0.5873	0.4388	0.2489	0.060*
C7	0.4357 (2)	0.5930 (2)	0.20912 (15)	0.0488 (4)
C8	0.3129 (2)	0.6118 (2)	0.11922 (16)	0.0553 (5)
H8	0.2618	0.6991	0.1277	0.066*
C9	0.2674 (2)	0.5063 (2)	0.02115 (16)	0.0550 (5)
H9	0.1854	0.5228	−0.0358	0.066*
C10	0.4820 (2)	0.7038 (2)	0.31119 (16)	0.0547 (5)
C11	0.5983 (3)	0.6827 (3)	0.40268 (19)	0.0699 (6)
C12	0.4142 (2)	0.8429 (3)	0.32460 (16)	0.0595 (5)
C13	0.7386 (3)	0.2441 (4)	0.4765 (2)	0.1005 (9)
H13A	0.7287	0.3532	0.5007	0.151*
H13B	0.7832	0.2031	0.5380	0.151*
H13C	0.6314	0.1796	0.4344	0.151*
C14	0.8517 (2)	0.2386 (3)	0.40876 (15)	0.0615 (6)
C15	0.9129 (2)	0.1013 (3)	0.38115 (16)	0.0603 (5)
H15	0.8838	0.0116	0.4054	0.072*
C16	1.0148 (2)	0.0970 (2)	0.31919 (15)	0.0516 (5)
H16	1.0558	0.0049	0.3019	0.062*
C17	1.0016 (2)	0.3596 (2)	0.30954 (15)	0.0541 (5)
H17	1.0331	0.4484	0.2851	0.065*
C18	0.9013 (2)	0.3681 (3)	0.37146 (16)	0.0608 (5)
H18	0.8649	0.4629	0.3894	0.073*
C19	1.1638 (2)	0.2155 (2)	0.21295 (15)	0.0556 (5)
H19A	1.2619	0.1790	0.2478	0.067*
H19B	1.1990	0.3218	0.2043	0.067*
C20	1.0766 (2)	0.1027 (2)	0.10308 (15)	0.0463 (4)
C21	1.1573 (2)	−0.0062 (2)	0.05873 (16)	0.0536 (5)
H21	1.2635	−0.0118	0.0980	0.064*
C22	0.9181 (2)	0.1069 (2)	0.04324 (15)	0.0537 (5)
H22	0.8614	0.1788	0.0722	0.064*
N1	0.4125 (2)	0.0106 (2)	−0.13825 (15)	0.0691 (5)
N2	0.0727 (3)	0.3070 (2)	−0.25956 (17)	0.0860 (7)
N3	0.3576 (3)	0.9543 (2)	0.33418 (17)	0.0811 (6)
N4	0.6931 (3)	0.6641 (3)	0.47670 (18)	0.1053 (8)
N5	1.05663 (17)	0.22537 (17)	0.28280 (11)	0.0450 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0510 (10)	0.0456 (11)	0.0541 (12)	0.0084 (9)	0.0109 (9)	0.0147 (9)
C2	0.0663 (13)	0.0334 (10)	0.0669 (14)	0.0076 (9)	0.0044 (11)	0.0116 (10)
C3	0.0517 (10)	0.0386 (10)	0.0582 (12)	0.0100 (8)	0.0089 (9)	0.0170 (9)
C4	0.0477 (10)	0.0360 (9)	0.0550 (11)	0.0079 (8)	0.0131 (9)	0.0154 (9)
C5	0.0449 (10)	0.0412 (10)	0.0595 (12)	0.0126 (8)	0.0129 (9)	0.0171 (9)
C6	0.0451 (10)	0.0483 (11)	0.0552 (12)	0.0115 (8)	0.0091 (9)	0.0170 (9)
C7	0.0455 (10)	0.0453 (10)	0.0563 (12)	0.0085 (8)	0.0160 (9)	0.0149 (9)
C8	0.0569 (11)	0.0444 (11)	0.0645 (13)	0.0195 (9)	0.0148 (10)	0.0133 (10)
C9	0.0552 (11)	0.0450 (11)	0.0607 (13)	0.0171 (9)	0.0060 (10)	0.0170 (10)
C10	0.0542 (11)	0.0528 (12)	0.0578 (12)	0.0164 (9)	0.0174 (10)	0.0119 (10)
C11	0.0687 (14)	0.0693 (15)	0.0610 (15)	0.0259 (11)	0.0103 (12)	−0.0010 (11)
C12	0.0608 (12)	0.0614 (14)	0.0584 (13)	0.0173 (11)	0.0207 (10)	0.0136 (11)
C13	0.0858 (17)	0.130 (2)	0.0825 (18)	0.0091 (16)	0.0458 (15)	0.0010 (16)
C14	0.0526 (11)	0.0783 (15)	0.0427 (11)	0.0085 (10)	0.0121 (9)	−0.0015 (10)
C15	0.0645 (12)	0.0624 (13)	0.0504 (12)	0.0020 (10)	0.0153 (10)	0.0179 (10)
C16	0.0573 (11)	0.0398 (10)	0.0558 (12)	0.0097 (8)	0.0135 (9)	0.0137 (9)
C17	0.0651 (12)	0.0447 (11)	0.0493 (11)	0.0178 (9)	0.0093 (10)	0.0130 (9)
C18	0.0618 (12)	0.0584 (13)	0.0556 (13)	0.0218 (10)	0.0106 (10)	0.0042 (10)
C19	0.0538 (11)	0.0557 (12)	0.0555 (12)	0.0047 (9)	0.0199 (10)	0.0105 (10)
C20	0.0470 (10)	0.0473 (10)	0.0496 (11)	0.0104 (8)	0.0197 (9)	0.0165 (8)
C21	0.0462 (10)	0.0610 (12)	0.0566 (12)	0.0184 (9)	0.0149 (9)	0.0180 (10)
C22	0.0551 (11)	0.0543 (12)	0.0576 (12)	0.0216 (9)	0.0234 (10)	0.0120 (10)
N1	0.0723 (11)	0.0566 (11)	0.0773 (13)	0.0242 (9)	0.0182 (10)	0.0145 (9)
N2	0.0910 (14)	0.0543 (11)	0.0851 (14)	0.0136 (10)	−0.0172 (12)	0.0205 (10)
N3	0.0905 (14)	0.0739 (13)	0.0845 (14)	0.0362 (11)	0.0307 (12)	0.0143 (11)
N4	0.1095 (17)	0.1122 (18)	0.0688 (14)	0.0548 (15)	−0.0072 (13)	−0.0060 (13)
N5	0.0505 (8)	0.0400 (8)	0.0415 (8)	0.0092 (7)	0.0110 (7)	0.0083 (7)

C1—N1	1.145 (2)	C13—H13B	0.9600
C1—C3	1.415 (3)	C13—H13C	0.9600
C2—N2	1.146 (2)	C14—C18	1.379 (3)
C2—C3	1.419 (3)	C14—C15	1.391 (3)
C3—C4	1.406 (3)	C15—C16	1.358 (3)
C4—C5	1.413 (2)	C15—H15	0.9300
C4—C9	1.419 (2)	C16—N5	1.344 (2)
C5—C6	1.359 (2)	C16—H16	0.9300
C5—H5	0.9300	C17—N5	1.337 (2)
C6—C7	1.416 (2)	C17—C18	1.347 (3)
C6—H6	0.9300	C17—H17	0.9300
C7—C8	1.412 (3)	C18—H18	0.9300
C7—C10	1.413 (3)	C19—N5	1.477 (2)
C8—C9	1.353 (3)	C19—C20	1.507 (3)
C8—H8	0.9300	C19—H19A	0.9700
C9—H9	0.9300	C19—H19B	0.9700
C10—C11	1.406 (3)	C20—C22	1.383 (2)
C10—C12	1.412 (3)	C20—C21	1.380 (2)
C11—N4	1.146 (3)	C21—C22i	1.380 (3)
C12—N3	1.141 (2)	C21—H21	0.9300
C13—C14	1.497 (3)	C22—C21i	1.380 (3)
C13—H13A	0.9600	C22—H22	0.9300
N1—C1—C3	178.6 (2)	C18—C14—C15	116.78 (18)
N2—C2—C3	178.5 (2)	C18—C14—C13	122.2 (2)
C4—C3—C2	121.18 (16)	C15—C14—C13	121.1 (2)
C4—C3—C1	123.07 (16)	C16—C15—C14	120.68 (19)
C2—C3—C1	115.72 (17)	C16—C15—H15	119.7
C3—C4—C5	122.03 (16)	C14—C15—H15	119.7
C3—C4—C9	121.27 (16)	N5—C16—C15	120.27 (18)
C5—C4—C9	116.70 (17)	N5—C16—H16	119.9
C6—C5—C4	121.22 (16)	C15—C16—H16	119.9
C6—C5—H5	119.4	N5—C17—C18	120.89 (19)
C4—C5—H5	119.4	N5—C17—H17	119.6
C5—C6—C7	122.16 (17)	C18—C17—H17	119.6
C5—C6—H6	118.9	C17—C18—C14	121.10 (19)
C7—C6—H6	118.9	C17—C18—H18	119.4
C8—C7—C10	121.36 (17)	C14—C18—H18	119.4
C8—C7—C6	116.30 (17)	N5—C19—C20	112.18 (14)
C10—C7—C6	122.33 (17)	N5—C19—H19A	109.2
C9—C8—C7	121.90 (17)	C20—C19—H19A	109.2
C9—C8—H8	119.1	N5—C19—H19B	109.2
C7—C8—H8	119.1	C20—C19—H19B	109.2
C8—C9—C4	121.70 (17)	H19A—C19—H19B	107.9
C8—C9—H9	119.1	C22—C20—C21	118.33 (17)
C4—C9—H9	119.1	C22—C20—C19	121.95 (17)
C11—C10—C12	117.16 (18)	C21—C20—C19	119.70 (16)
C11—C10—C7	122.08 (17)	C20—C21—C22i	120.67 (17)
C12—C10—C7	120.74 (18)	C20—C21—H21	119.7
N4—C11—C10	179.3 (2)	C22i—C21—H21	119.7
N3—C12—C10	179.1 (2)	C20—C22—C21i	121.00 (17)
C14—C13—H13A	109.5	C20—C22—H22	119.5
C14—C13—H13B	109.5	C21i—C22—H22	119.5
H13A—C13—H13B	109.5	C17—N5—C16	120.25 (16)
C14—C13—H13C	109.5	C17—N5—C19	120.70 (15)
H13A—C13—H13C	109.5	C16—N5—C19	119.05 (15)
H13B—C13—H13C	109.5
C2—C3—C4—C5	179.72 (17)	C18—C14—C15—C16	−0.8 (3)
C1—C3—C4—C5	1.8 (3)	C13—C14—C15—C16	179.7 (2)
C2—C3—C4—C9	0.1 (3)	C14—C15—C16—N5	−0.6 (3)
C1—C3—C4—C9	−177.77 (18)	N5—C17—C18—C14	−0.3 (3)
C3—C4—C5—C6	179.13 (17)	C15—C14—C18—C17	1.3 (3)
C9—C4—C5—C6	−1.2 (2)	C13—C14—C18—C17	−179.2 (2)
C4—C5—C6—C7	0.0 (3)	N5—C19—C20—C22	46.7 (2)
C5—C6—C7—C8	1.0 (3)	N5—C19—C20—C21	−134.85 (17)
C5—C6—C7—C10	−179.94 (18)	C22—C20—C21—C22i	0.7 (3)
C10—C7—C8—C9	−179.89 (19)	C19—C20—C21—C22i	−177.80 (17)
C6—C7—C8—C9	−0.8 (3)	C21—C20—C22—C21i	−0.7 (3)
C7—C8—C9—C4	−0.4 (3)	C19—C20—C22—C21i	177.76 (17)
C3—C4—C9—C8	−178.94 (18)	C18—C17—N5—C16	−1.2 (3)
C5—C4—C9—C8	1.4 (3)	C18—C17—N5—C19	178.69 (17)
C8—C7—C10—C11	176.93 (19)	C15—C16—N5—C17	1.7 (3)
C6—C7—C10—C11	−2.1 (3)	C15—C16—N5—C19	−178.25 (16)
C8—C7—C10—C12	−4.2 (3)	C20—C19—N5—C17	−110.79 (18)
C6—C7—C10—C12	176.78 (18)	C20—C19—N5—C16	69.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···N3ii	0.93	2.62	3.320 (3)	132
C17—H17···N2iii	0.93	2.47	3.204 (3)	136
C19—H19A···N3ii	0.97	2.57	3.394 (3)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯N3i	0.93	2.62	3.320 (3)	132
C17—H17⋯N2ii	0.93	2.47	3.204 (3)	136
C19—H19A⋯N3i	0.97	2.57	3.394 (3)	143

Symmetry codes: (i) ; (ii) .